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WO1997017328A1 - Pyridylacetic acid derivatives, method and intermediate products for producing them and agents containing them - Google Patents

Pyridylacetic acid derivatives, method and intermediate products for producing them and agents containing them Download PDF

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Publication number
WO1997017328A1
WO1997017328A1 PCT/EP1996/004676 EP9604676W WO9717328A1 WO 1997017328 A1 WO1997017328 A1 WO 1997017328A1 EP 9604676 W EP9604676 W EP 9604676W WO 9717328 A1 WO9717328 A1 WO 9717328A1
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WIPO (PCT)
Prior art keywords
alkyl
alkylamino
formula
alkoxy
hetaryl
Prior art date
Application number
PCT/EP1996/004676
Other languages
German (de)
French (fr)
Inventor
Bernd Müller
Hubert Sauter
Herbert Bayer
Wassilios Grammenos
Thomas Grote
Reinhard Kirstgen
Klaus Oberdorf
Franz Röhl
Norbert Götz
Michael Rack
Ruth Müller
Gisela Lorenz
Eberhard Ammermann
Siegfried Strathmann
Volker Harries
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to DE59605803T priority Critical patent/DE59605803D1/en
Priority to EP96937262A priority patent/EP0876344B1/en
Priority to AU74941/96A priority patent/AU7494196A/en
Priority to US09/068,002 priority patent/US5965587A/en
Priority to AT96937262T priority patent/ATE195729T1/en
Priority to JP9517797A priority patent/JPH11514658A/en
Publication of WO1997017328A1 publication Critical patent/WO1997017328A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to pyridylacetic acid derivatives of the formula I.
  • Y is oxygen or NR '
  • R ' is hydrogen or -C ⁇ C 4 alkyl
  • n 0, 1 or 2, where the radicals R can be different if m is 2;
  • R 1 is hydrogen and C ! -C 4 alkyl
  • R 2 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
  • R 3 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
  • cyclic radicals can in turn be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxy:, aminocarbonyl, aminothiocarbonyl, Ci-C ⁇ - alkyl, Ci-C ⁇ -haloalkyl, C ⁇ -C 6 alkylsulfonyl, C ⁇ -C 6 alkylsulfoxyl, C 3 C 6 cycloalkyl, Ci-C ⁇ -alkoxy, C 6 haloalkoxy, C ⁇ ⁇ C 6 alkoxycarbonyl, -C-C 6 alkylthio, Ci-C ⁇ -alkylamino, di-C ⁇ -C 6 -alkylamino, Ci-Ce-alkylarninocarbonyl, di-Ci-C ⁇ -alkylammocarbonyl, Ci-C ⁇ -alkylaminothiocarbon
  • Groups in turn can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C ⁇ -alkyl, Ci-C ⁇ - halo- genalkyl, C ⁇ -C 6 alkylsulfonyl, C ⁇ -C 6 alkylsulfoxyl, C 3 -C 6 cloalkyl -Cy-, C ⁇ -C6 alkoxy, Ci-C ⁇ -haloalkoxy, C ⁇ -C 6 alkyloxy carbonyl, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylamino, di-C 1 -C 6 -alkylamino, C 1 -C 6 -alkylaminocarbonyl, di-C 1 -C 6 -alkylaminocarbonyl, C 1 -C 6 -alky
  • A represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or -CC 6 alkyl
  • D represents a direct bond, oxygen or NR h ;
  • n 0 or 1
  • R a is hydrogen or Ci-C ⁇ -alkyl
  • R b is hydrogen or -CC 6 alkyl
  • R f is hydrogen, hydroxy, -CC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C ⁇ -alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 -Alkynyloxy, -CC 6 -alkoxy -CC 6 -alkyl, -C 6 -alkoxy-C 6 -C 6 -alkoxy and -C 6 -alkoxycarbonyl;
  • R9 independently of one another hydrogen, Cj . -C 6 alkyl, C 2 -C 6 ⁇ alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C6 cycloalkenyl, aryl, aryl-Ci-C ⁇ - alkyl, Hetaryl and hetaryl -CC 6 alkyl mean;
  • the invention also relates to processes and intermediates for the preparation of these compounds and compositions containing them for controlling animal pests and harmful fungi.
  • Phenylacetic acid derivatives for pest control are known from the literature (EP-A 422 597; EP-A 463 488; EP-A 370 629; EP-A 460 575; EP-A 472 300; WO-A 90 / 07,493; WO- A 92 / 13,830;
  • the present invention was based on new compounds with improved activity as an object.
  • L 1 in formula II stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Sodium hydride, potassium hydroxide, potassium carbonate and triethylamine according to the methods described in Houben-Weyl, vol. E 14b, p. 370f and Houben-Weyl, vol. 10/1, p. 1189f.
  • a base e.g. Sodium hydride, potassium hydroxide, potassium carbonate and triethylamine according to the methods described in Houben-Weyl, vol. E 14b, p. 370f and Houben-Weyl, vol. 10/1, p. 1189f.
  • the required hydroxyimim III is obtained, for example, by reacting a corresponding dihydroxyimine IV with a nucleophilically substituted reagent VI
  • III L 2 in the formula VI represents a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p. 385f; Houben-Weyl, Vol. 10/4, p. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, pp. 780f, described methods.
  • a base e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine
  • the compounds I can also be obtained by first reacting the benzyl derivative II with the dihydroxyimino derivative IV into a corresponding benzyloxime of the formula V, V then being converted to I with the nucleophilically substituted reagent VI.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. 10/1,
  • a base e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. 10/1,
  • Q ⁇ in formula IXb stands for the anion of an acid, in particular an inorganic acid, for example halide such as chloride.
  • reaction is carried out in a manner known per se in an inert organic solvent according to that described in EP-A 513 580; Houben-Weyl, Vol. 10/4, pp. 73f; Houben-Weyl, vol. E 14b, p. 369f and p. 385f.
  • the compounds I can also be obtained by first reacting the benzyl derivative II with the carbonylhydroxyimino derivative VII into a corresponding benzyloxyimine of the formula VIII, VIII then being converted to I with the hydroxylamine IXa or its salt IXb.
  • reaction is carried out in a manner known per se in an inert organic solvent according to the methods described in EP-A 463 488, DE-Anm. No. 42 28 867.3 methods described.
  • the required carbonyl compound VIa is obtained, for example, by reacting a corresponding hydroxyiminocarbonyl compound VII with a nucleophilically substituted reagent VI
  • R 4 L 2 0 C (R 3 ) - • C (R 2 ) - NOH
  • the compounds I can also be obtained by first reacting the benzylhydroxylamine Ila with the hydroxyimino derivative VII into the corresponding benzyloxyimino derivative of the formula V, V then being converted to I with the nucleophilically substituted reagent VI as described above.
  • the compounds I can also be prepared by first converting the benzylhydroxylamine Ila with the dicarbonyl derivative of the formula VIIIb into the benzyloxyimino derivative of the formula VIII and then VIII with the hydroxylamine IXa or its salt IXb is reacted to I as described above.
  • R 2 and / or R 3 represent a halogen atom are obtained from the corresponding precursors in which the radical in question represents a hydroxyl group by methods known per se (cf. Houben-Weyl, vol. E5, P. 631; J. Org. Chem. 36, 233 (1971); J. Org. Chem. 57, 3245 (1992)).
  • the corresponding reactions to the halogen derivative are preferably carried out at stages I and VIII.
  • the compounds I in which Y represents oxygen (IA) are obtained also by adding a methylpyridinecarboxylic acid ester of the general formula X in a manner known per se in the corresponding methylene pyridinecarboxylic acid ester of the general formula XI, wherein Shark stands for chlorine or bromine, converted, XI then converted into the corresponding pyridinecarboxylic acid ester of the general formula XII by reaction with a hydroxyimine of the formula III, XII reduced to the alcohol XIII, XIII oxidized to the pyridine aldehyde XIV, XIV in a manner known per se Converted into the cyanohydrin XV, XV then hydrolyzed to the corresponding mandelic acid ester XVI, XVI oxidized to the ⁇ -ketoester XVII and XVII then in a known manner either a) with O-methylhydroxylamine (H 2 NOCH 3 )
  • R x in formula X is -C 4 alkyl, especially methyl and ethyl.
  • Shark in the formula XI represents a halogen atom such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, in particular bromine.
  • This halogenation from X to XI usually takes place at temperatures of 20 ° C. to 160 ° C., preferably 40 ° C. to 130 ° C., in an inert organic solvent with a halogenating agent in the presence of a radical initiator or under irradiation with high-energy light [cf. Organikum, 15th ed. 1976, VEB Berlin, p. 196].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and Di
  • the halogenating agents are generally used in equimolar amounts or in excess or, if appropriate, as solvents.
  • Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, such as lithium hydride Potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic
  • alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium
  • alkyl magnesium halides such as methyl magnesium chloride
  • alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and
  • Dimethoxymagnesium also organic bases, e.g. tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Sodium hydroxide, potassium hydroxide and pyridine are particularly preferred.
  • the bases are generally set in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • Peroxides or azo compounds are generally used as radical initiators, particularly preferably dibenzoyl peroxide and azobisisobutyronitrile.
  • the radical initiators are usually used in catalytic amounts. In general, excess radical initiators are not troublesome.
  • UV light or light of a wavelength in the visible range can be used as high-energy light.
  • the compounds II can be prepared by the process described in item 5, starting from this process with derivatives in which the side chain is protected by an alkoxy, aryloxy or acyloxy protective group and then the protective group litera ⁇ known methods [cf. T. Greene, Protective Groups in Organic Synthesis, J. Wiley & Sons, 1981] in the last procedural step.
  • This reaction of XI with III to XII usually takes place at temperatures from 0 ° C. to 100 ° C., preferably 20 ° C. to 60 ° C., in an inert organic solvent in the presence of a base.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and di
  • the bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride Kalium ⁇ hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate as well as alkali metal bicarbonates such as sodium hydrogen carbonate, organometallic compounds, especially alkali metal alkyls such as methyl lithium, butyllithium alkyl and phenyllithium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide and aluminum hal
  • the bases are generally set in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and di
  • Metal hydrides are generally used as reducing agents. Lithium aluminum hydride and sodium borohydride are particularly suitable.
  • the reducing agents can generally be used in equimolar amounts or in excess.
  • the oxidation from XIII to XIV usually takes place at temperatures from 0 ° C to 60 ° C, preferably 10 ° C to 40 ° C in an inert organic solvent with a conventional oxidizing agent [cf. Organikum, 15th ed. 1976, pp. 443-44 7, 604-607, VEB, Berlin], particularly preferably with sodium hypochlorite solution in the presence of tetramethylpyridine-1-oxide.
  • a conventional oxidizing agent cf. Organikum, 15th ed. 1976, pp. 443-44 7, 604-607, VEB, Berlin
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloro- form and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert. -Butanol and dimethyl sulfoxide
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.
  • Inorganic compounds are generally used as cyanides. Sodium cyanide or potassium cyanide are particularly suitable.
  • the cyanides can generally be used at least in equimolar amounts, usually even in excess.
  • Inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride, ammonium chloride and zinc are found as acids and acid catalysts -Il-chloride, as well as organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
  • the acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the hydrolysis from XV to XVI takes place via the imido ester XVa as an intermediate (X "means an anion such as halide or sulfate).
  • the conversion from XV to XVa usually takes place at temperatures from -30 ° C. to 70 ° C., preferably at 0 ° C. to 30 ° C. in an inert organic solvent or in the alcohol R 1 -OH in the presence of an acid.
  • Suitable solvents for the reaction from XV to XVa are aliphatic hydrocarbons such as pentane, HExan, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene,
  • Ethers such as diethyl ether, diisopropyl ether, tert. -Butylmethyle ⁇ ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert. - butyl methyl ketone,
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-
  • Inorganic acids such as hydrofluoric acid, hydrochloric acid,
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II chloride
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
  • the acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the hydrolysis from XV to XVI usually takes place at temperatures from 0 ° C. to 100 ° C., preferably 40 ° C. to 100 ° C., in an inert organic solvent in the presence of an acid.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as
  • acids and acidic catalysts there are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II -chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
  • inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II -chloride
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
  • the acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the imidoester hydrohalide is hydrolyzed in water without further addition of acid.
  • This oxidation from XVI to XVII usually takes place according to that in point 5d. mentioned procedures. 5h.
  • the reaction of the ⁇ -keto ester XVII with O-methylhydroxylamine (H 2 NOCH 3 ) or an O-methylhydroxylammonium salt usually takes place at temperatures from 0 ° C to 60 ° C, preferably 20 ° C to 40 ° C according to [cf. EP-A 534 216].
  • reaction of the ⁇ -keto ester XVII with an ethylene-Wittig or -Wittig-Horner reagent usually takes place at temperatures from -30 ° C. to 60 ° C., preferably 10 ° C. to 40 ° C. according to EP-A 534 216 in an inert organic solvent in the presence of a base.
  • reaction of the ⁇ -keto ester XVII with a methoxy-Wittig or -Wittig-Horner reagent usually takes place at temperatures from -30 ° C to 60 ° C, preferably 10 ° C to 40 ° C according to EP-A 534 216 in the presence of a base.
  • the reaction of the ester IA with the amine is usually carried out at from 0 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C. in accordance with EP-A 534 216 in an inert organic solvent.
  • the reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products chromatographically.
  • Conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
  • the E isomers of the compounds I are preferred in terms of their activity (configuration based on the 0CH 3 or CH 3 group in relation to the COYR 1 group).
  • Alkyl straight or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, e.g. Ci-C ⁇ -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
  • ftlk ⁇ larci is an amino group which carries a straight-chain or branched alkyl group having 1 to 6 carbon atoms as mentioned above; Dialkyl, an, i ⁇ .p; an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 6 carbon atoms as mentioned above;
  • Alkylcarbonyl straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkylsulfonyl straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-S0 2 -);
  • AIVylapinocarbonyl alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the structure via a carbonyl group (-CO-);
  • Dialkylaminocarbonyl Dialkylamino groups each with 1 to
  • Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluor ⁇ methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluor ⁇ ethyl, 2, 2-dichloro-2-fluoroethyl, 2,2, 2-trichloroethyl and pentafluoroethyl;
  • Alkoxy straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-0-), for example C 1 -C 6 -alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, Butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy, 1, 1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy, 2,2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1, 1-dimethylpropyloxy, 1, 2-dimethylpropyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1, 1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,
  • Haloalkoxy straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the skeleton via an oxygen atom;
  • Alkylthio straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g. Cx-C ⁇ -alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2-dirnethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-di
  • Cycloalkyl monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • Alkenyloxy straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-0-);
  • Alkenylthio or alkenvlamino straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which (alkenylthio) are bonded to the skeleton via a sulfur atom or (alkenylamino) a nitrogen atom.
  • Alkenylcarbonyl straight-chain or branched alkenyl groups with 35 2 to 10 carbon atoms and a double bond in any position, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkynyl straight-chain or branched alkynyl groups with 2 to 40 10 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl , 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl -2-propynyl, 45 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1-methyl-3-pentynyl, l-methyl-4-pentynyl,
  • Alkynylcarbonyl straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in any position, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Cvcloalkenvl or Cvcloalkenvloxv Cvcloalkenvlthio and Cvclo- monocyclic alkenyl groups with 3 to 6 carbon ring members which are bonded to the skeleton directly or (cycloalkenyloxy) via an oxygen atom or (cycloalkenylthio) via a nitrogen atom (cycloalkenylthio), for example cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
  • Heterocvclvl or Heterocvclyloxv. Heterocyclylthio and HeterogYC-.Y-.Miil.PT three- to six-membered, saturated or partially unsaturated mono- or polycyclic heterocycles, which contain one to three herero atoms selected from a group consisting of oxygen, nitrogen and sulfur, and which directly or (heterocyclyloxy) via an oxygen atom or (heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a nitrogen atom, such as, for example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofurany1, 2-tetrahydrothienyl,
  • Arvlcarbonvl and Arvlsulfonvl aromatic mono- or polycyclic hydrocarbon radicals which directly or (aryloxy) via an oxygen atom (-0-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-C0-) or (arylsulfonyl) via a Sulfonyl group (-S0 2 -) are bound to the skeleton, for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals,
  • Hetaryl or hetaryloxy Hetarylthio. Hetarylcarbonyl and hetarylsulfonyl; aromatic mono- or polycyclic residues which in addition to carbon ring members additionally one to four
  • Nitrogen atoms or one to three nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom can contain and which directly or (hetaryloxy) via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S- ), (Hetarylcarbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group (-S0 2 -) are bound to the skeleton, for example
  • 5- ⁇ liedri ⁇ es heteroaryl. containing one to three nitrogen atoms 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-triazol-3-yl and 1,3,4-triazol-2- yl;
  • 5- ⁇ l-lower heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one May contain sulfur or oxygen atom or an oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-0xazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,
  • 5- ⁇ liedri ⁇ es heteroaryl bound via nitrogen containing one to four nitrogen atoms. or benzo-fused 5- ⁇ liedri ⁇ es heteroaryl bound via nitrogen. containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent one
  • Carbon ring member can be bridged by a buta-1, 3-diene-1,4-diyl group, these rings being bonded to the framework via one of the nitrogen ring members;
  • 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazin-2-yl, 1, 2, 4-triazin-3-yl and 1,2,4, 5-tetrazin-3-yl;
  • 6-ring heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline,
  • T aromatic mono- or polycyclic radicals which in addition to carbon ring members can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are bonded to the structure via a nitrogen atom.
  • R 2 is C 1 -C 4 -alkyl, in particular methyl.
  • R 2 is C 1 -C 4 alkoxy, in particular methoxy.
  • R 2 represents halogen, in particular chlorine.
  • R 3 is aryl, in particular, if appropriate, subst. Phenyl.
  • compounds I are particularly preferred, in which R 3 is alkyl, especially Ci-C ⁇ -alkyl stands.
  • R 3 is cycloalkyl, in particular C 3 -C 6 ⁇ cycloalkyl.
  • R 3 for aryloxyalkyl in particular in the phenyl part, if appropriate, subst. Phenoxy -C-C 2 alkyl, is.
  • R 3 is hetaryl, in particular, if appropriate, subst. Thienyl, isoxazolyl, pyrazolyl and pyridinyl.
  • R 4 is C 3 -C 6 alkenyl, in particular allyl.
  • R 4 is C 3 -C 6 -alkynyl, in particular propargyl.
  • R 4 for arylalkyl in particular in the phenyl part, if appropriate, subst.
  • Phenyl-C ⁇ C 2 alkyl stands.
  • R 4 represents haloalkenyl, in particular trans-chloroallyl.
  • R 4 is alkoxyalkyl, in particular C 1 -C 2 alkoxy-C 1 -C 2 alkyl.
  • compounds I are preferred in which the CfsOO-COYR 1 radical is bonded in the 2-position of the pyridyl ring.
  • the compounds I are suitable as fungicides.
  • the compounds I are distinguished by an excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers , Beans and pumpkin plants, as well as on the seeds of these plants. 5
  • Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, üncinula necator on vines, 0 Pucciniao species on cereals, 0 Pucciniao species on cereals and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various Plants, Plas
  • the compounds I are used by the fungi or the plants, seeds,
  • Materials or the soil are treated with a fungicidally effective amount of the active ingredients. It is used before or after the infection of the materials, plants or seeds by the fungi.
  • formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compounds according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine) , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • other active compounds for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • the fungicidal activity spectrum is enlarged in many cases.
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylene diamine bis-dithiocarbamate, tetramethylthiurium dibiammamodisulfide ), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl disulfide;
  • Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalic acid - di-isopropyl ester;
  • heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) phosphinyl] -3-phenyl-l, 2, 4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,2,2-tetrachloroethyl
  • fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N -furoyl (2) - alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacety1) -alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl -D, L-2-amino-butyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5-dichlorophenyl) -2, 4-dioxo-1,3-
  • the compounds of the formula I are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
  • the harmful insects include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticuluraura, chorumobistana, Cheata- ri forumana, Cheimatobella, Cheimatobella occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molest
  • dipterous insects for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria Contarinia sorghicola, Cordylobia, anthropogenic pophaga, Culex pipiens, Dacus cucurbitae, oleae Dacus, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cupata, Lucilia serata Lycoria pe
  • Thrips for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
  • From the order of the hymenoptera for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • Heteroptera For example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularisis, Lygus pratidularisis, Neopara solatularisis, Pies Thyanta perditor.
  • bugs Heteroptera
  • Acrosternum hilare for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularisis
  • suckers for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypy, Dreianafiaisolumiaia, Dreianafusiaolaia, Dreianafusiaolaia, Dreyfusiaolaia Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida
  • Orthoptera From the order of the straight wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum. Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
  • Orthoptera for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rub
  • arachnids such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shedelodi, iodine eroniophus, Iotetroniiuncus, Iotetranyius, Iotetronii Ixodes rubicundus, Ornithodorus moubata Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcop
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stick and leaf wholes, e.g.
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stick and leaf wholes, e.g.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range.
  • active ingredients are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • the amount of active ingredient used to control pests is 0.1 to 2.0, preferably 0.2 to 1.0, kg / ha under field conditions.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with Formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid and 10 parts by weight of the sodium salt
  • VIII.20 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay,
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • a mixture of 60 g (0.296 mol) of 2,4-dichloropropiophenone in 500 ml of toluene is mixed at -10 to -20 ° C. with 81 ml of saturated ethereal hydrochloric acid solution and then at the same temperature with a solution of 33.3 g (0.323 mol) of 2,4-dichloropropiophenone in 150 ml of ether.
  • the reaction mixture is then stirred for 4 hours at -10 ° C. and for 14 hours at room temperature. Then the reaction mixture is extracted with ice water and then five times with NaOH.
  • the combined al 'quay phases are based on 20% sulfuric acid Acidified to pH 5, the product crystallizing out.
  • the solid is filtered off and dissolved in methylene chloride and the organic phase is dried over MgSO 4 and concentrated.
  • the residue obtained is 63.1 g (42%) of the title compound as a light solid.
  • the active ingredients were given as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight.
  • % Emulphor® EL Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) is prepared and diluted with water in accordance with the desired concentration.
  • Leaves of potted vines of the "Müller-Thurgau" variety were sprayed with an aqueous spray mixture which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.
  • the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara vi ticola. Thereafter, the vines were first placed for 48 hours in a steam-saturated chamber at 24 ° C. and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.
  • Emulphor® EL Emulphor® EL, emulsifier based on ethoxylated fatty alcohols

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Abstract

The invention concerns pyridylacetic acid derivatives of formula (I), in which the substituents and the index have the following meanings: X - NOCH3, CHOCH3, CHCH3 and CHCH2CH3; Y - oxygen or NR', R' representing hydrogen or alkyl; R - cyano, nitro, trifluoromethyl, halogen, alkyl and alkoxy; m is 0, 1 or 2; R1 is hydrogen and alkyl; R2 - hydrogen, cyano, nitro, hydroxy, amino, halogen, alkyl, alkyl halide, alkoxy, alkoxy halide, alkyl thio, alkylamino or dialkylamino; R3 - hydrogen, cyano, nitro, hydroxy, amino, halogen; or optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio, alkenylamino, N-alkenyl-N-alkylamino, alkinyl, alkinyloxy, alkinylthio, alkinylamino, N-alkinyl-N-alkylamino, cycloalkyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, N-cycloalkyl-N-alkylamino, cycloalkenyl, cycloalkenyloxy, cycloalkenylthio, cycloalkenylamino, N-cycloalkenyl-N-alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino, N-heterocyclyl-N-alkylamino,aryl, aryloxy, arylthio,arylamino, N-aryl-N-alkylamino, hetaryl, hetaryloxy, hetarylthio, hetarylamino, and N-hetaryl-N-alkylamino; R4 - hydrogen, optionally substituted alkyl, alkenyl, alkinyl, alkylcarbonyl, alkenylcarbonyl, alkinylcarbonyl, alkylsulphonyl, cycloalkyl, aryl, arylcarbonyl, arylsulphonyl, hetaryl, hetarylcarbonyl, or hetarylsulphonyl. Also disclosed are the salts of the above derivatives,and methods and intermediate products for producing them and agents containing them.

Description

Pyridylessigsaurederivate, Verfahren und Zwischenprodukte zu ihrer Herstellung und sie enthaltende Mittel Pyridylacetic acid derivatives, processes and intermediates for their preparation and compositions containing them
Beschreibungdescription
Die vorliegende Erfindung betrifft Pyridylessigsaurederivate der Formel IThe present invention relates to pyridylacetic acid derivatives of the formula I.
Figure imgf000003_0001
in der die Substituenten und der Index die folgende Bedeutung haben:
Figure imgf000003_0001
in which the substituents and the index have the following meaning:
X NOCH3, CHOCH3, CHCH3 und CHCH2CH3;X NOCH 3 , CHOCH 3 , CHCH 3 and CHCH 2 CH 3 ;
Y Sauerstoff oder NR' ;Y is oxygen or NR ';
R' Wasserstoff oder Cι~C4-Alkyl;R 'is hydrogen or -C ~ C 4 alkyl;
R Cyano, Nitro, Trifluormethyl, Halogen, Cι-C4-Alkyl und Cι-C4-Alkoxy;R cyano, nitro, trifluoromethyl, halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy;
m 0, 1 oder 2, wobei die Reste R verschieden sein können, wenn m für 2 steht;m is 0, 1 or 2, where the radicals R can be different if m is 2;
R1 Wasserstoff und C!-C4-Alkyl;R 1 is hydrogen and C ! -C 4 alkyl;
R2 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Halogen,R 2 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
Cι-C4-Alkyl, Cι-C4-Halogenalkyl, Cι~C4-Alkoxy, Cι-C<j-Halogen- alkoxy, Cι-C4-Alkylthio, Cι-C4-Alkylamino oder Di-Cι-C4-alkyl- amino;Cι-C 4 -alkyl, C 4 haloalkyl, Cι ~ C 4 -alkoxy, C <j-halo- alkoxy, Cι-C 4 alkylthio, Cι-C 4 alkylamino or di-Cι-C 4- alkylamino;
R3 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Halogen,R 3 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
Cι-C6-Alkyl, Cι-C6-Alkoxy, Ci-Cß-Alkylthio, Ci-Cβ-Alkylamino, Di-Cι-C6-alkylamino, C2-C6-Alkenyl, C2-C6-Alkenyloxy,Cι-C 6 -alkyl, C 6 alkoxy, Ci-CSS-alkylthio, Ci-Cβ alkylamino, di-Cι-C 6 -alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy ,
C2-C6-Alkenylthio, C2-C6-Alkenylamino, N-C2-C6-Alkenyl- N-Ci-Cδ-alkylamino, C2-C6 _Alkinyl, C2-C6-Alkinyloxy, C2-C6-Alkinylthio, C2-C6-Alkinylamino, N-C2-C6-Alkinyl- N-Ci-Cδ-alkylamino, wobei die Kohlenwasserstoffreste dieser Gruppen partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Reste tragen können: Cyano, Nitro, Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Ci-Cδ-Alkylaminocarbonyl, Di-Ci-Cβ-alkylaminocarbonyl, Ci-Cg-Alkylaminothiocarbonyl, Di-Cι-C6-alkylaminothiocarbonyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, Cι-C6-Alkoxy, Cι-C6-Halogenalkoxy, Cι-C6-Alkoxycarbonyl, Ci-Cβ-Alkylthio, Cι-C6-Alkylamino, Di-Cι-C6-alkylamino, C2-C6-Alkenyloxy, C3-C6-Cycloalkyl, C3-C6-Cycloalkyloxy, Heterocyclyl, Heterocyclyloxy, Aryl, Aryloxy, Aryl-Cι-C4-alkoxy, Arylthio, Aryl-Cι-C4-alkylthio, Hetaryl, Hetaryloxy, Hetaryl-Cι~C4-alkoxy, Hetarylthio, Heta- ryl-Cj.-C4-alkylthio, wobei die cyclischen Reste ihrerseits partiell oder vollständig halogeniert sein können und/oder ein bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxy: , Aminocarbonyl, Aminothiocarbonyl, Ci-Cβ-Alkyl, Ci-Cβ-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl , C3C6-Cycloalkyl, Ci-Cδ-Alkoxy, Cι-C6-Halogenalkoxy, Cι~C6-Alkoxycarbonyl, Cι-C6-Alkylthio, Ci-Cδ-Alkylamino, Di-Cι-C6-alkylamino, Ci-Ce-Alkylarninocarbonyl, Di-Ci-Cβ-alkylammocarbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Cι-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6~Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio und C(=N0Ra)-An-Rb;C 2 -C 6 alkenylthio, C 2 -C 6 alkenylamino, NC 2 -C 6 alkenyl- N-Ci-Cδ-alkylamino, C 2 -C 6 _ alkynyl, C 2 -C 6 alkynyloxy, C 2 -C 6 -alkynylthio, C 2 -C 6 -alkynylamino, NC 2 -C 6 -alkynyl-N-Ci-Cδ-alkylamino, where the hydrocarbon radicals of these groups can be partially or completely halogenated or can carry one to three of the following radicals : Cyano, Nitro, Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, halogen, Ci-Cδ-alkylaminocarbonyl, di-Ci-Cβ-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Cι-C 6 -alkylaminothiocarbonyl, Cι-C 6 -alkylsulfonyl, Cι-C 6 -alkylsulfoxyl, Cι-C 6 -alkoxy, -C-C 6 -haloalkoxy, -C-C 6 -alkoxycarbonyl, Ci-Cβ-alkylthio, -C-C 6 -alkylamino, di-Cι-C 6 -alkylamino, C 2 -C 6 -alkenyloxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl -CC 4 alkoxy, arylthio, aryl -CC 4 -alkylthio, hetaryl, hetaryloxy, hetaryl-Cι ~ C 4 alkoxy, hetarylthio, hetaryl-Cj . -C 4 -alkylthio, where the cyclic radicals can in turn be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxy:, aminocarbonyl, aminothiocarbonyl, Ci-Cβ- alkyl, Ci-Cβ-haloalkyl, Cι-C 6 alkylsulfonyl, Cι-C 6 alkylsulfoxyl, C 3 C 6 cycloalkyl, Ci-C δ -alkoxy, C 6 haloalkoxy, Cι ~ C 6 alkoxycarbonyl, -C-C 6 alkylthio, Ci-C δ -alkylamino, di-Cι-C 6 -alkylamino, Ci-Ce-alkylarninocarbonyl, di-Ci-Cβ-alkylammocarbonyl, Ci-Cβ-alkylaminothiocarbonyl, di-Cι-C 6 - alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 ~ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NO R a ) -A n -R b ;
C3-C6-Cycloalkyl, C3-C6-Cycloalkyloxy, C3-C6-Cycloalkylthio, C3-C6-Cycloalkylamino, N-C3-C6-Cycloalkyl-N-Cι-C6-alkylamino, C3-C6-Cycloalkenyl, C3-C6-Cycloalkenyloxy, C3-C6-Cycloalke- nylthio, C3-C6-Cycloalkenylamino, N-C3-C6~Cycloalkenyl- N-Ci-Cβ-alkylamino, Heterocyclyl, Heterocyclyloxy, Heterocy¬ clylthio, Heterocyclylamino, N-Heterocyclyl-N-Ci-Cδ-alkyl- amino, Aryl, Aryloxy, Arylthio, Arylamino, N-Aryl-C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, C 3 -C 6 cycloalkylamino, NC 3 -C6 cycloalkyl-N-Cι-C 6 alkylamino, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -cycloalkenyloxy, C 3 -C 6 -cycloalkenyl-nio, C 3 -C 6 -cycloalkenylamino, NC 3 -C6 ~ cycloalkenyl- N-Ci-Cβ-alkylamino, heterocyclyl, heterocyclyloxy , Heterocyclylthio, heterocyclylamino, N-heterocyclyl-N-Ci-C δ -alkylamino, aryl, aryloxy, arylthio, arylamino, N-aryl-
N-Cι-C6-alkylamino, Hetaryl, Hetaryloxy, Hetarylthio, Hetary- lamino, N-Hetaryl-N-Ci-Cβ-alkylamino, wobei die cyclischen Re¬ ste partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl,N-C 1 -C 6 -alkylamino, hetaryl, hetaryloxy, hetarylthio, hetarylamino, N-hetaryl-N-Ci-Cβ-alkylamino, where the cyclic radicals can be partially or completely halogenated or one to three of the following groups can wear: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl,
Aminothiocarbonyl, Halogen, Ci-Ce-Alkyl, Cι-C6-Halogenalkyl, Ci-Cβ-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, Cj-Cβ-Halogenalkoxy, Cι-C6-Alkoxycarbonyl, Cι-C6-Alkylthio, Ci-Cß-Alkylamino, Di-Cι-C6-alkylamino, Cι-C6-Alkylaminocarbonyl, Di-Cι-C6-alkylaminocarbonyl,Aminothiocarbonyl, halogen, Ci-Ce-alkyl, Cι-C 6 haloalkyl, Ci-Cβ-alkylsulfonyl, Cι-C 6 alkylsulfoxyl, C 3 -C 6 cycloalkyl, Cι-C 6 alkoxy, Cj-Cβ-haloalkoxy , -C-C 6 -alkoxycarbonyl, -C-C 6 -alkylthio, Ci-C ß -alkylamino, di-Cι-C 6 -alkylamino, Cι-C 6 -alkylaminocarbonyl, di-Cι-C 6 -alkylaminocarbonyl,
Cι-C6-Alkylaminothiocarbonyl, Di-Cι-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy, C(=N0Ra)-An-Rb oder NRf-CO-D-R9;C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy, C (= N0R a ) -A n -R b or NR f -CO-D-R9;
Wasserstoff, Cι-Cιo-Alkyl, C2-Cι0-Alkenyl, C2-Cι0-Alkinyl, Cι-C10-Alkyl- carbonyl, C2-C10-Alkenylcarbonyl, C3-Cι0-Alkinylcarbonyl oder Cι-Cιo-Alkylsulfonyl, wobei diese Reste partiell oder voll¬ ständig halogeniert sein können oder einen bis drei der fol- genden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mer¬ capto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, Cι-C6-Alkoxy, Cι-C6-Halogenalkoxy, Ci-Cδ-Alkoxycarbonyl, Cι-C6-Alkylthio, Cx-Cβ-Alkylamino, Di-Cι-C6-alkylamino, Ci-Cβ-Alkylaminocarbonyl, Di-Cι-C6-alkyl- aminocarbonyl, Ci-Cδ-Alkylaminothiocarbonyl, Di-Ci-Cδ-alkyl- aminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, C3-C6-Cycloalkyl, C3-C6-Cycloalkyloxy, Heterocyclyl, Hetero¬ cyclyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy und Hetarylthio, wobei die cyclischenHydrogen, -C-Cιo-alkyl, C 2 -Cι 0 -alkenyl, C 2 -Cι 0 -alkynyl, Cι-C 10 -alkylcarbonyl, C 2 -C 10 -alkenylcarbonyl, C 3 -Cι 0 -alkynylcarbonyl or Cι-Cιo Alkylsulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 -Alkyl, -C-C 6 -haloalkyl, Cι-C 6 -alkylsulfonyl, Cι-C 6 -alkylsulfoxyl, Cι-C 6 -alkoxy, Cι-C 6 -haloalkoxy, Ci-C δ -alkoxycarbonyl, Cι-C 6 - Alkylthio, Cx-Cβ-alkylamino, di-Cι-C 6 -alkylamino, Ci-Cβ-alkylaminocarbonyl, di-Cι-C 6 -alkyl-aminocarbonyl, Ci-C δ -alkylaminothiocarbonyl, di-Ci-C δ -alkyl- aminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, heterocyclyl, heterocyclicloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, Hetaryl, hetaryloxy and hetarylthio, the cyclic
Gruppen ihrerseits partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen kön¬ nen: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Amino¬ carbonyl, Aminothiocarbonyl, Halogen, Ci-Cβ-Alkyl, Ci-Cβ-Halo- genalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C3-C6-Cy- cloalkyl, Cι-C6-Alkoxy, Ci-Cβ-Halogenalkoxy, Cι-C6-Alkyloxy- carbonyl, Cι-C6-Alkylthio, Cι-C6-Alkylamino, Di-Cι~C6-Alkyl- amino, Cι-C6-Alkylaminocarbonyl, Di-Cι-C6-Alkylaminocarbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Cι-C6-Alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio oderGroups in turn can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Ci-Cβ- halo- genalkyl, Cι-C 6 alkylsulfonyl, Cι-C 6 alkylsulfoxyl, C 3 -C 6 cloalkyl -Cy-, Cι-C6 alkoxy, Ci-Cβ-haloalkoxy, Cι-C 6 alkyloxy carbonyl, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylamino, di-C 1 -C 6 -alkylamino, C 1 -C 6 -alkylaminocarbonyl, di-C 1 -C 6 -alkylaminocarbonyl, C 1 -C 6 -alkylaminothiocarbonyl, di-Cι -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or
C(=NORa)-An-Rb;C (= NOR a ) -A n -R b ;
C3-C6-Cycloalkyl, Aryl, Arylcarbonyl, Arylsulfonyl, Hetaryl, Hetarylcarbonyl oder Hetarylsulfonyl, wobei diese Reste par¬ tiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hy¬ droxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothio¬ carbonyl, Halogen, Ci-Cβ-Alkyl, Ci-Cβ-Halogenalkyl, Ci-Cβ-Al- kylcarbonyl, Ci-Cß-Alkylsulfonyl, Cj-Cβ-Alkylsulfoxyl, C3-C6-Cycloalkyl, Ci-Cβ-Alkoxy, Cj.-C6-Halogenalkoxy, Ci-Cβ-Alkyloxycarbonyl, Ci-Cβ-Alkylthio, Ci-Cβ-Alkylamino, Di-Ci-Cβ-Alkylamino, Ci-Cβ-Alkylaminocarbonyl, Di-Ci-Cβ-Alkyl- aminocarbonyl, Cι-C6-Alkylaminothiocarbonyl, Di-Ci-Ce-Alkyl- aminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl,C 3 -C 6 cycloalkyl, aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto , Amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, Ci-Cβ-alkylcarbonyl, Ci-C ß- alkylsulfonyl, Cj-Cβ-alkylsulfoxyl, C 3 -C 6- cycloalkyl, Ci-Cβ-alkoxy, Cj.-C 6 -haloalkoxy, Ci-Cβ-alkyloxycarbonyl, Ci-Cβ-alkylthio, Ci-Cβ-alkylamino, di-Ci-Cβ-alkylamino, Ci-Cβ-alkylaminocarbonyl, Di-Ci-Cβ-alkyl aminocarbonyl, -C-C 6 alkylaminothiocarbonyl, di-Ci-Ce-alkyl aminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C6 alkenyloxy, benzyl,
Benzyloxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy, C(=NORa)-An-Rb oder NRf-CO-D-R9;Benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy, C (= NOR a ) -A n -R b or NR f -CO-D-R9;
wobei A für Sauerstoff, Schwefel oder Stickstoff steht und wobei der Stickstoff Wasserstoff oder Cι~C6-Alkyl trägt;in which A represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or -CC 6 alkyl;
D eine direkte Bindung, Sauerstoff oder NRh bedeutet;D represents a direct bond, oxygen or NR h ;
n 0 oder 1 bedeutet;n represents 0 or 1;
Ra Wasserstoff oder Ci-Cβ-Alkyl bedeutet undR a is hydrogen or Ci-Cβ-alkyl and
Rb Wasserstoff oder Cι-C6-Alkyl bedeutet,R b is hydrogen or -CC 6 alkyl,
Rf Wasserstoff, Hydroxy, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alki- nyl, Ci-Cβ-Alkoxy, C2-C6-Alkenyloxy, C2-C6-Alkinyloxy, Cι-C6-Alkoxy-Cι-C6-alkyl, Cι-C6-Alkoxy-Cι-C6-alkoxy und Cι-C6-Alkoxycarbonyl bedeutet;R f is hydrogen, hydroxy, -CC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-Cβ-alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 -Alkynyloxy, -CC 6 -alkoxy -CC 6 -alkyl, -C 6 -alkoxy-C 6 -C 6 -alkoxy and -C 6 -alkoxycarbonyl;
R9, Rh unabhängig voneinander Wasserstoff, Cj.-C6-Alkyl, C2-C6~Alke- nyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl, C3-C6-Cycloalkenyl, Aryl, Aryl-Ci-Cδ-alkyl, Hetaryl und Hetaryl-Cι-C6-alkyl bedeu- ten;R9, Rh independently of one another hydrogen, Cj . -C 6 alkyl, C 2 -C 6 ~ alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C6 cycloalkenyl, aryl, aryl-Ci-C δ- alkyl, Hetaryl and hetaryl -CC 6 alkyl mean;
sowie deren Salze.as well as their salts.
Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung dieser Verbindungen sowie sie enthaltende Mittel zur Bekämpfung tierischer Schädlinge und Schadpilze.The invention also relates to processes and intermediates for the preparation of these compounds and compositions containing them for controlling animal pests and harmful fungi.
Aus der Literatur sind Phenylessigsäurederivate zur Schädlings¬ bekämpfung bekannt (EP-A 422 597; EP-A 463 488; EP-A 370 629; EP-A 460 575; EP-A 472 300; WO-A 90/07,493; WO-A 92/13,830;Phenylacetic acid derivatives for pest control are known from the literature (EP-A 422 597; EP-A 463 488; EP-A 370 629; EP-A 460 575; EP-A 472 300; WO-A 90 / 07,493; WO- A 92 / 13,830;
WO-A 92/18,487; WO-A 95/18,789; WO-A 95/21,153; WO-A 95/21,154; WO-A 95/21,156) .WO-A 92 / 18,487; WO-A 95 / 18,789; WO-A 95 / 21,153; WO-A 95 / 21,154; WO-A 95 / 21,156).
Der vorliegenden Erfindung lagen neue Verbindungen mit verbesser- ter Wirkung als Aufgabe zugrunde.The present invention was based on new compounds with improved activity as an object.
Demgemäß wurden die eingangs definierten Pyridylessigsaurederi¬ vate I gefunden. Außerdem wurden Verfahren und Zwischenprodukte zu ihrer Herstellung sowie sie enthaltende Mittel zur Bekämpfung von tierischen Schädlingen und Schadpilzen und ihre Verwendung in diesem Sinne gefunden.We have found that this object is achieved by the pyridylacetic acid derivatives I defined at the outset. In addition, processes and intermediates for their preparation and compositions containing them for controlling animal pests and harmful fungi and their use were found in this sense.
Die Verbindungen I sind auf verschiedenen Wegen nach an sich in der Literatur bekannten Verfahren erhältlich. Grundsätzlich ist es bei der Synthese der Verbindungen I unerheb¬ lich, ob zunächst die Gruppierung -C(X)-C02R1 oder die Gruppierung -CH20N=C(R2)-C(R3)=N0R4 aufgebaut wird.The compounds I can be obtained in various ways by processes known per se in the literature. In the synthesis of the compounds I, it is fundamentally irrelevant whether the grouping -C (X) -C0 2 R 1 or the grouping -CH 2 0N = C (R 2 ) -C (R 3 ) = NOR 4 is initially established becomes.
Der Aufbau der Gruppierung -C(X)-C02R1 ist beispielsweise aus der eingangs zitierten Literatur bekannt.The structure of the grouping -C (X) -C0 2 R 1 is known, for example, from the literature cited at the beginning.
Die Art der Synthese der -CH2ON=C(R2)-C(R3)=NOR4 Seitenkette richtet sich im wesentlichen nach der Art der Substituenten R2 und R3.The type of synthesis of the -CH 2 ON = C (R 2 ) -C (R 3 ) = NOR 4 side chain depends essentially on the type of the substituents R 2 and R 3 .
1. Für den Fall, daß R2 und R3 nicht Halogen bedeuten, geht man beim Aufbau der Gruppierung -CH20N=C(R2)-C(R3)=NOR4 im all¬ gemeinen so vor, daß man ein Benzylderivat der Formel II mit einem Hydroxyimim der Formel III umsetzt.1. In the event that R 2 and R 3 do not mean halogen, the structure of the grouping -CH 2 0N = C (R 2 ) -C (R 3 ) = NOR 4 is generally carried out in such a way that reacting a benzyl derivative of the formula II with a hydroxyimime of the formula III.
R4ON=C( L1 R 4 ON = C ( L1
Figure imgf000007_0001
Figure imgf000007_0001
IIII
Figure imgf000007_0002
Figure imgf000007_0002
L1 in der Formel II steht für eine nukleophil austauschbare Abgangsgruppe, z.B. Halogen oder Sulfonatgruppen, vorzugs¬ weise Chlor, Brom, lod, Mesylat, Tosylat oder Triflat.L 1 in formula II stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base, z.B. Natriumhydrid, Kaliumhydroxid, Kaliumcarbonat und Tri¬ ethylamin gemäß den in Houben-Weyl, Bd. E 14b, S. 370f und Houben-Weyl, Bd. 10/1, S. 1189f beschriebenen Methoden.The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Sodium hydride, potassium hydroxide, potassium carbonate and triethylamine according to the methods described in Houben-Weyl, vol. E 14b, p. 370f and Houben-Weyl, vol. 10/1, p. 1189f.
Das benötigte Hydroxyimim III erhält man beispielsweise durch Umsetzung eines entsprechenden Dihydroxyimins IV mit einem nukleophil substituierten Reagens VIThe required hydroxyimim III is obtained, for example, by reacting a corresponding dihydroxyimine IV with a nucleophilically substituted reagent VI
R4 L1 + HON=C(R3) C(R2) =NOHR 4 L 1 + HON = C (R 3 ) C (R 2 ) = NOH
VI IVVI IV
R4ON=C(R3)- C(R2) =NOHR 4 ON = C (R 3 ) - C (R 2 ) = NOH
III L2 in der Formel VI steht für eine nukleophil austauschbare Abgangsgruppe, z.B. Halogen oder Sulfonatgruppen, vorzugs¬ weise Chlor, Brom, Iod, Mesylat, Tosylat oder Triflat.III L 2 in the formula VI represents a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base, z.B. Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid, Pyridin und Triethylamin gemäß den in Houben-Weyl, Bd. E 14b, S. 307f, S. 370f und S. 385f; Houben-Weyl, Bd. 10/4, S. 55f, S. 180f und S. 217f; Houben-Weyl, Bd. E 5, S. 780f, beschrie¬ benen Methoden.The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p. 385f; Houben-Weyl, Vol. 10/4, p. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, pp. 780f, described methods.
1.1 Alternativ können die Verbindungen I auch dadurch erhalten werden, daß das Benzylderivat II zunächst mit dem Dihydroxy- iminoderivat IV in ein entsprechendes Benzyloxim der Formel V umgesetzt wird, wobei V anschließend mit dem nukleophil substituierten Reagens VI zu I umgesetzt wird.1.1 Alternatively, the compounds I can also be obtained by first reacting the benzyl derivative II with the dihydroxyimino derivative IV into a corresponding benzyloxime of the formula V, V then being converted to I with the nucleophilically substituted reagent VI.
Figure imgf000008_0001
Figure imgf000008_0001
IIII
Figure imgf000008_0003
Figure imgf000008_0003
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base z.B. Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid, Pyridin und Triethylamin gemäß den in Houben-Weyl, Bd. 10/1,The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. 10/1,
S. 1189f; Houben-Weyl, Bd. E 14b, S. 307f, S. 370f undPp. 1189f; Houben-Weyl, vol. E 14b, p. 307f, p. 370f and
S. 385f; Houben-Weyl, Bd. 10/4, S. 55f, S. 180f und S. 217f;P. 385f; Houben-Weyl, Vol. 10/4, p. 55f, p. 180f and p. 217f;
Houben-Weyl, Bd. E 5, S. 780f, beschriebenen Methoden. 1.2 Analog ist es ebenfalls möglich, das benötigte Hydroxyimim der Formel III aus einem Carbonylhydroxyimin VII durch Umset¬ zung mit einem Hydroxylamin IXa oder seinem Salz IXb herzu¬ stellen.Houben-Weyl, vol. E 5, p. 780f. 1.2 Analogously, it is also possible to prepare the required hydroxyimim of the formula III from a carbonylhydroxyimine VII by reaction with a hydroxylamine IXa or its salt IXb.
(R2) =NOH(R 2 ) = NOH
Figure imgf000009_0001
Figure imgf000009_0001
R40N=C (R3) C (R2) = NOHR 4 0N = C (R 3 ) C (R 2 ) = NOH
IIIIII
Qθ in der Formel IXb steht für das Anion einer Säure, ins' besondere einer anorganischen Säure, z.B. Halogenid wie Chlorid.Q θ in formula IXb stands for the anion of an acid, in particular an inorganic acid, for example halide such as chloride.
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel gemäß den in EP-A 513 580; Houben-Weyl, Bd. 10/4, S. 73f; Houben-Weyl, Bd. E 14b, S. 369f und S. 385f beschriebenen Methoden.The reaction is carried out in a manner known per se in an inert organic solvent according to that described in EP-A 513 580; Houben-Weyl, Vol. 10/4, pp. 73f; Houben-Weyl, vol. E 14b, p. 369f and p. 385f.
1.3 Alternativ können die Verbindungen I auch dadurch erhalten werden, daß das Benzylderivat II zunächst mit dem Carbonyl- hydroxyiminoderivat VII in ein entsprechendes Benzyloxyimin der Formel VIII umgesetzt wird, wobei VIII anschließend mit dem Hydroxylamin IXa bzw. dessen Salz IXb zu I umgesetzt wird.1.3 Alternatively, the compounds I can also be obtained by first reacting the benzyl derivative II with the carbonylhydroxyimino derivative VII into a corresponding benzyloxyimine of the formula VIII, VIII then being converted to I with the hydroxylamine IXa or its salt IXb.
0=C(R3) C(R2) =NOH + Rm—fC "0~CH2 L1 0 = C (R 3 ) C (R 2 ) = NOH + Rm-fC "0 ~ C H 2 L 1
VII II COYR1 VII II COYR 1
Figure imgf000009_0002
Figure imgf000009_0002
COYR1 I Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel gemäß den in Houben-Weyl, Bd. E 14b, S. 369f; Houben-Weyl, Bd. 10/1, S. 1189f und Houben-Weyl, Bd. 10/4, S. 73f oder EP-A 513 580 beschriebenen Methoden.COYR 1 I The reaction is carried out in a manner known per se in an inert organic solvent according to the in Houben-Weyl, vol. E 14b, p. 369f; Houben-Weyl, vol. 10/1, p. 1189f and Houben-Weyl, vol. 10/4, p. 73f or EP-A 513 580.
1.4 Eine weitere Möglichkeit zur Herstellung der Verbindungen I ist die Umsetzung des Benzylderivats II mit N-Hydroxyphthal- imid und nachfolgender Hydrazinolyse zum Benzylhydroxylamin Ila und die weitere Umsetzung von Ila mit einer Carbonyl- Verbindung Vlla.1.4 Another possibility for the preparation of the compounds I is the reaction of the benzyl derivative II with N-hydroxyphthalimide and subsequent hydrazinolysis to give the benzylhydroxylamine Ila and the further reaction of Ila with a carbonyl compound VIIIa.
Figure imgf000010_0001
Figure imgf000010_0001
0=C(R2) C(R3)=NOR4 Ila0 = C (R 2 ) C (R 3 ) = NOR 4 Ila
VllaVlla
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel gemäß den in EP-A 463 488, DE-Anm. Nr. 42 28 867.3 beschriebenen Methoden.The reaction is carried out in a manner known per se in an inert organic solvent according to the methods described in EP-A 463 488, DE-Anm. No. 42 28 867.3 methods described.
Die benötigte Carbonylverbindung Vlla erhält man beispiels¬ weise durch Umsetzung einer entsprechenden Hydroxyimino- carbonylverbindung VII mit einem nukleophil substituierten Reagens VIThe required carbonyl compound VIa is obtained, for example, by reacting a corresponding hydroxyiminocarbonyl compound VII with a nucleophilically substituted reagent VI
R4 L2 0=C(R3)- •C(R2) — NOHR 4 L 2 0 = C (R 3 ) - • C (R 2 ) - NOH
VI VIIVI VII
0=C(R2) C(R3)=NOR4 0 = C (R 2 ) C (R 3 ) = NOR 4
Vlla oder durch Umsetzung einer entsprechenden DicarbonylVer¬ bindung Vllb mit einem Hydroxylamin IXa oder dessen Salz IXb
Figure imgf000011_0001
Vlla or by reacting a corresponding dicarbonyl compound Vllb with a hydroxylamine IXa or its salt IXb
Figure imgf000011_0001
0=C(R2) C(R3) =NOR4 0 = C (R 2 ) C (R 3 ) = NOR 4
VllaVlla
Die Umsetzungen erfolgen in an sich bekannter Weise in einem inerten organischen Lösungsmittel gemäß den in EP-A 513 580, Houben-Weyl, Bd. 10/4, S. 55f, S. 73f, S. 180f und S. 217f; Houben-Weyl, Bd. E 14b, S. 307f und 369f, Houben-Weyl, Bd. E 5, S. 780f beschriebenen Methoden.The reactions are carried out in a manner known per se in an inert organic solvent in accordance with the methods described in EP-A 513 580, Houben-Weyl, Vol. 10/4, p. 55f, p. 73f, p. 180f and p. 217f; Houben-Weyl, vol. E 14b, pp. 307f and 369f, Houben-Weyl, vol. E 5, pp. 780f.
1.5 Entsprechend können die Verbindungen I auch dadurch erhalten werden, daß das Benzylhydroxylamin Ila zunächst mit dem Hydroxyiminoderivat VII in das entsprechende Benzyloxyimino- derivat der Formel V umgesetzt wird, wobei V anschließend mit dem nukleophil substituierten Reagens VI wie vorstehend beschrieben zu I umgesetzt wird.1.5 Correspondingly, the compounds I can also be obtained by first reacting the benzylhydroxylamine Ila with the hydroxyimino derivative VII into the corresponding benzyloxyimino derivative of the formula V, V then being converted to I with the nucleophilically substituted reagent VI as described above.
Figure imgf000011_0002
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000011_0003
1.6 Analog können die Verbindungen I ebenfalls dadurch herge¬ stellt werden, daß das Benzylhydroxylamin Ila zunächst mit dem Dicarbonylderivat der Formel Vllb in das Benzyloxyimino- derivat der Formel VIII überführt wird und VIII anschließend mit dem Hydroxylamin IXa oder dessen Salz IXb wie vorstehend beschrieben zu I umgesetzt wird.1.6 Analogously, the compounds I can also be prepared by first converting the benzylhydroxylamine Ila with the dicarbonyl derivative of the formula VIIIb into the benzyloxyimino derivative of the formula VIII and then VIII with the hydroxylamine IXa or its salt IXb is reacted to I as described above.
0=C(R3) C(R2) = 0 -ttVβl.- 0NH2 0 = C (R 3 ) C (R 2 ) = 0 -ttVβl.- 0NH 2
VHb ιιa C rOYxR1 VHb ιι a C rOY x R 1
Figure imgf000012_0001
Figure imgf000012_0001
2. Verbindungen, in denen R2 und/oder R3 für ein Halogenatom stehen, erhält man aus den entsprechenden Vorstufen, in denen der betreffende Rest für eine Hydroxygruppe steht nach an sich bekannten Methoden (vgl. Houben-Weyl, Vol. E5, S. 631; J. Org. Chem. 36, 233 (1971); J. Org. Chem. 57, 3245 (1992)). Vorzugsweise werden die entsprechenden Umsetzungen zum Halogenderivat auf den Stufen I und VIII vorgenommen.2. Compounds in which R 2 and / or R 3 represent a halogen atom are obtained from the corresponding precursors in which the radical in question represents a hydroxyl group by methods known per se (cf. Houben-Weyl, vol. E5, P. 631; J. Org. Chem. 36, 233 (1971); J. Org. Chem. 57, 3245 (1992)). The corresponding reactions to the halogen derivative are preferably carried out at stages I and VIII.
3. Verbindungen, in denen R2 und/oder R3 über ein 0-, S- oder N-Atom an das Molekülgerüst gebunden sind, erhält man aus den entsprechenden Vorstufen, in denen der betreffende Rest für ein Halogenatom steht nach an sich bekannten Methoden (vgl. Houben-Weyl, Bd. E5, S. 826 f und 1280 f, J. Org. Chem. 36, 233 (1971), J. Org. Chem. 46, 3623 (1981)). Vorzugsweise werden die entsprechenden Umsetzungen der Halogenderivat auf den Stufen I und VIII vorgenommen.3. Compounds in which R 2 and / or R 3 are bonded to the molecular skeleton via a 0, S or N atom are obtained from the corresponding precursors in which the radical in question represents a halogen atom, as is known per se Methods (see Houben-Weyl, Vol. E5, pp. 826 f and 1280 f, J. Org. Chem. 36, 233 (1971), J. Org. Chem. 46, 3623 (1981)). The corresponding reactions of the halogen derivative are preferably carried out at stages I and VIII.
4. Verbindungen, in denen R2 und/oder R3 über ein Sauerstoffatom an das Molekül gebunden sind, erhält man zum Teil auch aus den entsprechenden Vorstufen, in denen der betreffende Rest für eine Hydroxygruppe steht nach an sich bekannten Methoden (vgl. Houben-Weyl, Bd. E5, S. 826-829, Aust. J. Chem. 22» 1341-9 (1974)). Vorzugsweise werden die entsprechenden Umsetzungen zu den Alkoxyderivaten auf den Stufen I und VIII vorgenommen. 5. Nach einem weiteren Verfahren erhält man die Verbindungen I, in denen Y für Sauerstoff steht (IA), auch dadurch, daß man einen Methylpyridincarbonsäureester der allgemeinen Formel X in an sich bekannter Weise in den entsprechenden Methylen- pyridincarbonsäureester der allgemeinen Formel XI, worin Hai für Chlor oder Brom steht, überführt, XI anschließend durch Umsetzung mit einem Hydroxyimin der Formel III in den ent¬ sprechenden Pyridincarbonsäureester der allgemeinen Formel XII überführt, XII zum Alkohol XIII reduziert, XIII zum Pyri- dinaldehyd XIV oxidiert, XIV in an sich bekannter Weise in das Cyanhydrin XV überführt, XV anschließend zum entsprechen¬ den Mandelsäureester XVI hydrolysiert, XVI zum α-Ketoester XVII oxidiert und XVII anschließend in an sich bekannter Weise entweder a) mit O-Methylhydroxylamin (H2NOCH3) oder einem O-Methyl- hydroxylammoniumsalz, oder b) mit einem Ethylen-Wittig- oder -wittig-Horner Reagens, oder c) mit einem Methoxy-Wittig- oder -Wittig-Horner-Reagens in den entsprechenden Pyridylessigsäureester IA überführt.4. Compounds in which R 2 and / or R 3 are bonded to the molecule via an oxygen atom are also obtained in part from the corresponding precursors in which the radical in question represents a hydroxyl group by methods known per se (cf. Houben -Weyl, Vol. E5, pp. 826-829, Aust. J. Chem. 22 »1341-9 (1974)). The corresponding reactions to the alkoxy derivatives are preferably carried out at stages I and VIII. 5. According to a further process, the compounds I in which Y represents oxygen (IA) are obtained also by adding a methylpyridinecarboxylic acid ester of the general formula X in a manner known per se in the corresponding methylene pyridinecarboxylic acid ester of the general formula XI, wherein Shark stands for chlorine or bromine, converted, XI then converted into the corresponding pyridinecarboxylic acid ester of the general formula XII by reaction with a hydroxyimine of the formula III, XII reduced to the alcohol XIII, XIII oxidized to the pyridine aldehyde XIV, XIV in a manner known per se Converted into the cyanohydrin XV, XV then hydrolyzed to the corresponding mandelic acid ester XVI, XVI oxidized to the α-ketoester XVII and XVII then in a known manner either a) with O-methylhydroxylamine (H 2 NOCH 3 ) or an O-methyl - hydroxylammonium salt, or b) with an ethylene-Wittig or -wittig-Horner reagent, or c) with a methoxy-Wittig o the -Wittig-Horner reagent is converted into the corresponding pyridylacetic acid ester IA.
Figure imgf000013_0001
Figure imgf000013_0001
OHOH
Figure imgf000013_0002
Figure imgf000013_0002
CNCN
Figure imgf000013_0003
Figure imgf000013_0003
C02R1
Figure imgf000014_0001
C0 2 R 1
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0002
Rx in der Formel X steht fürCι-C4-Alkyl, insbesondere Methyl und Ethyl.R x in formula X is -C 4 alkyl, especially methyl and ethyl.
Hai in der Formel XI steht für ein Halogenatom wie Fluor, Chlor, Brom und Iod, vorzugsweise Chlor und Brom, ins¬ besondere Brom.Shark in the formula XI represents a halogen atom such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, in particular bromine.
a. Diese Halogenierung von X nach XI erfolgt üblicherweise bei Temperaturen von 20°C bis 160°C, vorzugsweise 40°C bis 130°C in einem inerten organischen Lösungsmittel mit einem Halogenierungsmittel in Gegenwart eines Radikalstarters oder unter Bestrahlung mit energiereichem Licht [vgl . Organikum, 15. Aufl . 1976, VEB Berlin , S. 196] .a. This halogenation from X to XI usually takes place at temperatures of 20 ° C. to 160 ° C., preferably 40 ° C. to 130 ° C., in an inert organic solvent with a halogenating agent in the presence of a radical initiator or under irradiation with high-energy light [cf. Organikum, 15th ed. 1976, VEB Berlin, p. 196].
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halo¬ genierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Chlorbenzol, Methy¬ lenchlorid, Tetrachlorkohlenstoff und Cyclohexan. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and Dimethylformamide, particularly preferably chlorobenzene, methylene chloride, carbon tetrachloride and cyclohexane. Mixtures of the solvents mentioned can also be used.
Als Halogenierungsmittel finden allgemein anorganischeGenerally, inorganic halogenating agents are found
Verbindungen wie Chlor, Brom und Sulfurylchlorid Verwendung. Besonders geeignet sind aber auch organische Verbindungen wie N-Halogenide, insbesondere N-Bromsuccinimid.Compounds such as chlorine, bromine and sulfuryl chloride use. However, organic compounds such as N-halides, in particular N-bromosuccinimide, are also particularly suitable.
Die Halogenierungsmittel werden im allgemeinen äquimolar oder im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The halogenating agents are generally used in equimolar amounts or in excess or, if appropriate, as solvents.
Es kann vorteilhaft sein, die Halogenierung in Gegenwart ei- ner Base durchzuführen. Als Basen kommen allgemein anorgani¬ sche Verbindungen wie Alkalimetall- und Erdalkalimetall- hydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydro¬ xid und Kalziumhydroxid, Alkalimetall- und Erdalkalimetall- oxide wie Lithiumoxid, Natriumoxid, Kalziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Kalziumhydrid, Alkalimetallamide wie Lithiumamid, Natriumamid und Kalium- amid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithium- carbonat und Kalziumcarbonat sowie Alkalimetallhydrogen- carbonate wie Natriumhydrogencarbonat, metallorganischeIt may be advantageous to carry out the halogenation in the presence of a base. Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, such as lithium hydride Potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate, and alkali metal bicarbonates such as sodium bicarbonate, organometallic
Verbindungen, insbesondere Alkalimetallalkyle wie Methyl- lithium, Butyllithium und Phenyllithium, Alkylmagnesium- halogenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkoholate wie Natriummethanolat, Natrium- ethanolat, Kaliumethanolat, Kalium-tert.-Butanolat undCompounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and
Dimethoxymagnesium außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Tri-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Na¬ triumhydroxyd, Kaliumhydroxyd und Pyridin.Dimethoxymagnesium also organic bases, e.g. tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines. Sodium hydroxide, potassium hydroxide and pyridine are particularly preferred.
Die Basen werden im allgemeinen in katalytischen Mengen ei gesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally set in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
Als Radikalstarter finden allgemein Peroxide oder Azoverbin- dungen Verwendung, besonders bevorzugt Dibenzoylperoxid und Azobisisobutyronitril. Die Radikalstarter werden üblicher- weise in katalytischen Mengen verwendet. Im allgemeinen sind Überschüsse an Radikalstarter nicht störend. Als energiereiches Licht kann in Abhängigkeit vom verwendeten Halogenierungsmittel UV-Licht oder Licht von einer Wellen¬ länge im sichtbaren Bereich Verwendung finden.Peroxides or azo compounds are generally used as radical initiators, particularly preferably dibenzoyl peroxide and azobisisobutyronitrile. The radical initiators are usually used in catalytic amounts. In general, excess radical initiators are not troublesome. Depending on the halogenating agent used, UV light or light of a wavelength in the visible range can be used as high-energy light.
Die für die Herstellung der Verbindungen I benötigten Ausgangsstoffe II können analog dem in Punkt 5. beschriebenen Verfahren ausgehend von den Nicotinsäureestern der Formel X hergestellt werden, wobei vorzugsweise zuerst der Aufbau der Gruppierung -C(=X)-COYR1 und anschließend die Halogenierung erfolgt.The starting materials II required for the preparation of the compounds I can be prepared analogously to the process described in point 5, starting from the nicotinic acid esters of the formula X, preferably with the grouping -C (= X) -COYR 1 first followed by the halogenation .
Figure imgf000016_0001
Figure imgf000016_0001
XHIaXHIa
Figure imgf000016_0002
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0003
Außerdem können die Verbindungen II aus den Verbindungen I hergestellt werden, in denen die Gruppierung -0N=CR2-CR3=NOR4 nach der Methode der Benzyletherspaltung [vgl . T. Greene, Protective Groups in Organic Synthesis, J. Wiley & Sons, 1981] abgespalten wird (z.B. mit HBr, HCl oder BBr3) .In addition, the compounds II can be prepared from the compounds I in which the grouping -0N = CR 2 -CR 3 = NOR 4 by the benzyl ether cleavage method [cf. T. Greene, Protective Groups in Organic Synthesis, J. Wiley & Sons, 1981] is split off (e.g. with HBr, HCl or BBr 3 ).
Desweiteren können die Verbindungen II nach dem in Punkt 5. beschriebenen Verfahren hergestellt werden, indem man bei diesem Verfahren von Derivaten ausgeht, bei denen die Seiten¬ kette durch eine Alkoxy-, Aryloxy- oder Acyloxy-Schutzgruppe geschützt ist, und die Schutzgruppe anschließend nach litera¬ turbekannten Methoden [vgl . T. Greene, Protective Groups in Organic Synthesis, J. Wiley & Sons, 1981] im letzten Verfah¬ rensschritt abspaltet.Furthermore, the compounds II can be prepared by the process described in item 5, starting from this process with derivatives in which the side chain is protected by an alkoxy, aryloxy or acyloxy protective group and then the protective group litera¬ known methods [cf. T. Greene, Protective Groups in Organic Synthesis, J. Wiley & Sons, 1981] in the last procedural step.
Diese Umsetzung von XI mit III nach XII erfolgt üblicherweise bei Temperaturen von 0°C bis 100°C, vorzugsweise 20°C bis 60°C in einem inerten organischen Lösungsmittel in Gegenwart einer Base.This reaction of XI with III to XII usually takes place at temperatures from 0 ° C. to 100 ° C., preferably 20 ° C. to 60 ° C., in an inert organic solvent in the presence of a base.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halo¬ genierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Dimethylformamid, Ace¬ tonitril, tert.-Butylmethylether, Toluol und Wasser. Es kön- nen auch Gemische der genannten Lösungsmittel verwendet wer¬ den.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and dimethylformamide , particularly preferably dimethylformamide, acetonitrile, tert-butyl methyl ether, toluene and water. Mixtures of the solvents mentioned can also be used.
Als Basen kommen allgemein anorganische Verbindungen wie Al¬ kalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Kalziumhydroxid, Alkali- metall- und Erdalkalimetalloxide wie Lithiumoxid, Natrium¬ oxid, Kalziumoxid und Magnesiumoxid, Alkalimetall- und Erd¬ alkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kalium¬ hydrid und Kalziumhydrid, Alkalimetallamide wie Lithiumamid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkali- metallcarbonate wie Lithiumcarbonat und Kalziumcarbonat sowie Alkalimetallhydrogencarbonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetall- alkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumhalogenide wie Methylmagnesiumchlorid sowie Al¬ kalimetall- und Erdalkalimetallalkoholate wie Natrium- methanolat, Natriumethanolat, Kaliumethanolat, Kalium-tert.- Butanolat und Dirnethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Tri-iso- propylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt wer¬ den Natriumhydrid, Kaliumcarbonat, Natriummethanolat und Na- triumethanolat.The bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride Kalium¬ hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate as well as alkali metal bicarbonates such as sodium hydrogen carbonate, organometallic compounds, especially alkali metal alkyls such as methyl lithium, butyllithium alkyl and phenyllithium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide, as well as lithium magnesium halide and aluminum halide, - and alkaline earth metal alcoholates such as sodium methanolate, sodium ethanolate, potassium ethanolate, potassium tert.- Butanolate and Dirnethoxymagnesium, also organic bases, for example tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines. Sodium hydride, potassium carbonate, sodium methoxide and sodium ethanolate are particularly preferred.
Die Basen werden im allgemeinen in katalytischen Mengen ei gesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally set in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
c. Die Reduktion von XII nach XIII erfolgt üblicherweise beic. The reduction from XII to XIII usually takes place at
Temperaturen von -70°C bis 110°C, vorzugsweise 0°C bis 60°C in einem inerten organischen Lösungsmittel mit einem Reduktions¬ mittel.Temperatures from -70 ° C to 110 ° C, preferably 0 ° C to 60 ° C in an inert organic solvent with a reducing agent.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halo¬ genierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Toluol, Tetrahydrofuran und tert.-Butylmethylether. Es können auch Gemische der ge- nannten Lösungsmittel verwendet werden.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and dimethylformamide , particularly preferably toluene, tetrahydrofuran and tert-butyl methyl ether. Mixtures of the solvents mentioned can also be used.
Als Reduktionsmittel finden allgemein Metallhydride Verwen¬ dung. Besonders geeignet sind Lithiumaluminiumhydrid und Na¬ triumborhydrid. Die Reduktionsmittel können im allgemeinen äquimolar oder im Überschuß verwendet werden.Metal hydrides are generally used as reducing agents. Lithium aluminum hydride and sodium borohydride are particularly suitable. The reducing agents can generally be used in equimolar amounts or in excess.
d. Die Oxidation von XIII nach XIV erfolgt üblicherweise bei Temperaturen von 0°C bis 60°C, vorzugsweise 10°C bis 40°C in einem inerten organischen Lösungsmittel mit einem üblichen Oxidationsmittel [vgl . Organikum, 15. Aufl . 1976, S. 443-44 7, 604-607, VEB, Berlin] , besonders bevorzugt mit Natriumhypoch¬ lorit-Lösung in Gegenwart von Tetramethylpyridin-1-oxid.d. The oxidation from XIII to XIV usually takes place at temperatures from 0 ° C to 60 ° C, preferably 10 ° C to 40 ° C in an inert organic solvent with a conventional oxidizing agent [cf. Organikum, 15th ed. 1976, pp. 443-44 7, 604-607, VEB, Berlin], particularly preferably with sodium hypochlorite solution in the presence of tetramethylpyridine-1-oxide.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloro- form und Chlorbenzol, Ether wie Diethylether, Diisopropyl¬ ether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydro¬ furan, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethyl- keton, Alkohole wie Methanol, Ethanol, n-Propanol, Iso¬ propanol, n-Butanol und tert. -Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Methylenchlorid, Toluol, tert.-Butylmethylether und Wasser. Es können auch Ge¬ mische der genannten Lösungsmittel verwendet werden.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloro- form and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol and tert. -Butanol and dimethyl sulfoxide and dimethylformamide, particularly preferably methylene chloride, toluene, tert-butyl methyl ether and water. Mixtures of the solvents mentioned can also be used.
Diese Umsetzung von XIV nach XV erfolgt üblicherweise beiThis conversion from XIV to XV usually takes place at
Temperaturen von -10°C bis 50°C, vorzugsweise 0°C bis 30°C in einem inerten organischen Lösungsmittel mit einem Cyanid in Gegenwart einer Säure.Temperatures from -10 ° C to 50 ° C, preferably 0 ° C to 30 ° C in an inert organic solvent with a cyanide in the presence of an acid.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloro- form und Chlorbenzol, Ether wie Diethylether, Diisopropyl¬ ether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydro¬ furan, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethyl- keton, Alkohole wie Methanol, Ethanol, n-Propanol, Iso- propanol, n-Butanol und tert.-Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Diethylether, To¬ luol, tert.-Butylmethylether und Wasser. Es können auch Gemi¬ sche der genannten Lösungsmittel verwendet werden.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and dimethyl sulfoxide and dimethylformamide, particularly preferably diethyl ether, toluene, tert-butyl methyl ether and water. Mixtures of the solvents mentioned can also be used.
Als Cyanide finden allgemein anorganische Verbindungen Ver¬ wendung. Besonders geeignet sind Natriumcyanid oder Kalium- cyanid.Inorganic compounds are generally used as cyanides. Sodium cyanide or potassium cyanide are particularly suitable.
Die Cyanide können im allgemeinen mindestens äquimolar meist sogar im Überschuß verwendet werden.The cyanides can generally be used at least in equimolar amounts, usually even in excess.
Als Säuren und saure Katalysatoren finden anorganische Säuren wie Fluorwasserstoffsäure, Salzsäure, Bromwasserstoffsäure, Schwefelsäure und Perchlorsäure, Lewis-Säuren wie Bortri- fluorid, Aluminiumtrichlorid, Eisen-III-chlorid, Zinn-IV- chlorid, Titan-IV-chlorid, Ammoniumchlorid und Zink-Il-chlo- rid, sowie organische Säuren wie Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Zitronensäure und Trifluoressigsäure Verwendung. Die Säuren werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Über¬ schuß oder gegebenenfalls als Lösungsmittel verwendet werden. f . Die Hydrolyse von XV nach XVI erfolgt über den Imidoester XVa als Zwischenprodukt (X" bedeutet ein Anion wie z.B. Halogenid oder Sulfat) .Inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride, ammonium chloride and zinc are found as acids and acid catalysts -Il-chloride, as well as organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid. The acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent. f. The hydrolysis from XV to XVI takes place via the imido ester XVa as an intermediate (X "means an anion such as halide or sulfate).
Figure imgf000020_0001
Figure imgf000020_0001
R1 R 1
Die Umwandlung von XV nach XVa erfolgt üblicherweise bei Tem- peraturen von -30°C bis 70°C, vorzugsweise bei 0°C bis 30°C in einem inerten organischen Lösungsmittel oder in dem Alkohol R1-OH in Gegenwart einer Säure.The conversion from XV to XVa usually takes place at temperatures from -30 ° C. to 70 ° C., preferably at 0 ° C. to 30 ° C. in an inert organic solvent or in the alcohol R 1 -OH in the presence of an acid.
Geeignete Lösungsmittel für die Reaktion von XV nach XVa sind aliphatische Kohlenwasserstoffe wie Pentan, HExan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xy¬ lol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloro- form und Chlorbenzol,Suitable solvents for the reaction from XV to XVa are aliphatic hydrocarbons such as pentane, HExan, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene,
Ether wie Diethylether, Diisopropylether, tert. -Butylmethyle¬ ther, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert. - Butylmethylketon,Ethers such as diethyl ether, diisopropyl ether, tert. -Butylmethyle¬ ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert. - butyl methyl ketone,
Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-
Butanol und tert. -Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Diethylether, Toluol, Methanol und Ethanol.Butanol and tert. -Butanol as well as dimethyl sulfoxide and dimethylformamide, particularly preferably diethyl ether, toluene, methanol and ethanol.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.Mixtures of the solvents mentioned can also be used.
Als Säuren und saure Katalysatoren finden anorganische Säuren wie Fluorwasserstoffsäure, Salzsäure,Inorganic acids such as hydrofluoric acid, hydrochloric acid,
Bromwasserstoffsäure, Schwefelsäure und Perchlorsäure, Lewis- Säuren wie Bortrifluorid, Aluminiumtrichlorid, Eisen-III- chlorid, Zinn-IV-chlorid, Titan-IV-chlorid und Zink-II-chlo¬ rid, sowie organische Säuren wie Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Zitronensäure und Trifluoressigsäure Verwendung.Hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II chloride, as well as organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
Die Säuren werden im allgemeinen in katalytischen Mengen ein¬ gesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
Die Hydrolyse von XV nach XVI erfolgt üblicherweise bei Tem- peraturen von 0°C bis 100°C, vorzugsweise 40°C bis 100°C in einem inerten organischen Lösungsmittel in Gegenwart einer Säure.The hydrolysis from XV to XVI usually takes place at temperatures from 0 ° C. to 100 ° C., preferably 40 ° C. to 100 ° C., in an inert organic solvent in the presence of an acid.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloro¬ form und Chlorbenzol, Ether wie Diethylether, Diisopropyl¬ ether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydro- furan, Nitrile wie Acetonitril und Propionitril, Ketone wieSuitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as
Aceton, Methylethylketon, Diethylketon und tert.-Butylmethyl- keton, Alkohole wie Methanol, Ethanol, n-Propanol, Iso¬ propanol, n-Butanol und tert.-Butanol sowie Dimethylsulfoxid und Dimethylformamid, besonders bevorzugt Wasser, Methanol, Toluol und Acetonitril. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and dimethylformamide, particularly preferably water, methanol, toluene and acetonitrile. Mixtures of the solvents mentioned can also be used.
Als Säuren und saure Katalysatoren finden anorganische Säuren wie Fluorwasserstoffsäure, Salzsäure, Bromwasserstoffsäure, Schwefelsäure und Perchlorsäure, Lewis-Säuren wie Bortri- fluorid, Aluminiumtrichlorid, Eisen-III-chlorid, Zinn-IV- chlorid, Titan-IV-chlorid und Zink-II-chlorid, sowie organische Säuren wie Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Zitronensäure und Trifluoressigsäure Verwendung.As acids and acidic catalysts, there are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II -chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid.
Die Säuren werden im allgemeinen in katalytischen Mengen ein¬ gesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
Nach einer besonders bevorzugten Ausführungsform hydrolysiert man das Imidoester-hydrohalogenid in Wasser ohne weiteren Zu¬ satz von Säure.According to a particularly preferred embodiment, the imidoester hydrohalide is hydrolyzed in water without further addition of acid.
Diese Oxidation von XVI nach XVII erfolgt üblicherweise nach den bei Punkt 5d. genannten Verfahren. 5h. Die Umsetzung des α-Ketoesters XVII mit O-Methylhydroxylamin (H2NOCH3) oder einem O-Methylhydroxylammoniumsalz erfolgt üblicherweise bei Temperaturen von 0°C bis 60°C, vorzugsweise 20°C bis 40°C gemäß [ vgl . EP-A 534 216] .This oxidation from XVI to XVII usually takes place according to that in point 5d. mentioned procedures. 5h. The reaction of the α-keto ester XVII with O-methylhydroxylamine (H 2 NOCH 3 ) or an O-methylhydroxylammonium salt usually takes place at temperatures from 0 ° C to 60 ° C, preferably 20 ° C to 40 ° C according to [cf. EP-A 534 216].
5i. Die Umsetzung des α-Ketoesters XVII mit einem Ethylen-Wittig- oder -Wittig-Horner Reagens erfolgt üblicherweise bei Tempe¬ raturen von -30°C bis 60°C, vorzugsweise 10°C bis 40°C gemäß EP-A 534 216 in einem inerten organischen Lösungsmittel in Gegenwart einer Base.5i. The reaction of the α-keto ester XVII with an ethylene-Wittig or -Wittig-Horner reagent usually takes place at temperatures from -30 ° C. to 60 ° C., preferably 10 ° C. to 40 ° C. according to EP-A 534 216 in an inert organic solvent in the presence of a base.
5k. Die Umsetzung des α-Ketoesters XVII mit einem Methoxy-Wittig- oder -Wittig-Horner-Reagens erfolgt üblicherweise bei Tempe¬ raturen von -30°C bis 60°C, vorzugsweise 10°C bis 40°C gemäß EP-A 534 216 in Gegenwart einer Base.5k. The reaction of the α-keto ester XVII with a methoxy-Wittig or -Wittig-Horner reagent usually takes place at temperatures from -30 ° C to 60 ° C, preferably 10 ° C to 40 ° C according to EP-A 534 216 in the presence of a base.
6. Verbindungen der Formel I, in denen Y für NRa steht (IB) , erhält man aus den entsprechenden Verbindungen IA in an sich bekannter Weise durch Umsetzung mit einem Amin der Formel XVIII.6. Compounds of the formula I in which Y represents NR a (IB) are obtained from the corresponding compounds IA in a manner known per se by reaction with an amine of the formula XVIII.
Figure imgf000022_0001
Figure imgf000022_0001
Die Umsetzung des Esters IA mit dem Amin erfolgt üblicher¬ weise bei Temperaturen von 0°C bis 80°C, vorzugsweise 20°C bis 60°C gemäß EP-A 534 216 in einem inerten organischen Lösungs¬ mittel.The reaction of the ester IA with the amine is usually carried out at from 0 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C. in accordance with EP-A 534 216 in an inert organic solvent.
Die Reaktionsgemische werden in üblicher Weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenen- falls chromatographische Reinigung der Rohprodukte. DieZwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräun¬ licher, zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen. Die Verbindungen I können bei der Herstellung aufgrund ihrer C=C- und C=N-Doppelbindungen als E/Z-Isomerengemische anfallen, die z.B. durch Kristallisation oder Chromatographie in üblicher Weise in die Einzelverbindungen getrennt werden können.The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products chromatographically. The intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or purified under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting. Due to their C = C and C = N double bonds, the compounds I can be obtained in the form of E / Z isomer mixtures which, for example, can be separated into the individual compounds in the customary manner, for example by crystallization or chromatography.
Sofern bei der Synthese Isomerengemische anfallen, ist im allge¬ meinen jedoch eine Trennung nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säure- oder Baseneinwirkung) ineinander umwandeln können. EntsprechendeIf isomer mixtures are obtained in the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Appropriate
Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen in der behandelten Pflanze oder im zu bekämpfenden Schadpilz oder tierischen Schädling erfolgen.Conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
In Bezug auf die C=X-Doppelbindung werden hinsichtlich ihrer Wirksamkeit die E-Isomere der Verbindungen I bevorzugt (Konfi¬ guration bezogen auf die 0CH3 bzw. CH3-Gruppe im Verhältnis zur COYR1-Gruppe) .With regard to the C = X double bond, the E isomers of the compounds I are preferred in terms of their activity (configuration based on the 0CH 3 or CH 3 group in relation to the COYR 1 group).
In Bezug auf die -N=CR2-CR3=N-Doppelbindungen werden im allgemeinen hinsichtlich ihrer Wirksamkeit die cis-Isomere der Verbindungen I (Konfiguration bezogen auf den Rest R2 bzw. R3 im Verhältnis zur -OCH2- bzw. -OR4-Gruppe bzw. bezogen auf den Rest R4 im Verhältnis zur -N=CR2-Gruppe) bevorzugt.With regard to the -N = CR 2 -CR 3 = N double bonds, the cis isomers of the compounds I (configuration based on the radical R 2 or R 3 in relation to the -OCH 2 - or -OR 4 group or based on the radical R 4 in relation to the -N = CR 2 group) is preferred.
Bei der eingangs angegebenen Definitionen der Verbindungen I wurden Sammelbegriffe verwendet, die allgemein repräsentativ für die folgenden Gruppen stehen:In the definitions of the compounds I given at the outset, collective terms were used which are generally representative of the following groups:
HalgTtl.i Fluor, Chlor, Brom und Jod;HalgTtl.i fluorine, chlorine, bromine and iodine;
Alkyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 4, 6 oder 10 Kohlenstoffatomen, z.B. Ci-Cβ-Alkyl wie Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyl, 1-Ethylpropyl, Hexyl, 1, 1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methyl- pentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1, 2-Dimethylbutyl, 1, 3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1, 1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-l-methyl- propyl und 1- Ethyl-2-methylpropyl;Alkyl; straight or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, e.g. Ci-Cβ-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2- Trimethylpropyl, 1-ethyl-l-methylpropyl and 1-ethyl-2-methylpropyl;
ftlkΥlarciuflt eine Aminogruppe, welche eine geradkettige oder ver- zweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen wie vorstehend genannt trägt; Dialkyl,a-n,iτ.p; eine Aminogruppe, welche zwei voneinander unab¬ hängige, geradkettige oder verzweigte Alkylgruppen mit jeweils 1 bis 6 Kohlenstoffatomen wie vorstehend genannt, trägt;ftlkΥlarci is an amino group which carries a straight-chain or branched alkyl group having 1 to 6 carbon atoms as mentioned above; Dialkyl, an, iτ.p; an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 6 carbon atoms as mentioned above;
Alkylcarbonyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 10 Kohlenstoffatomen, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind;Alkylcarbonyl; straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkylsulfonyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 oder 10 Kohlenstoffatomen, welche über eine Sulfonyl¬ gruppe (-S02-) an das Gerüst gebunden sind;Alkylsulfonyl; straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-S0 2 -);
Alkvisulfoxyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, welche über eine Sulfoxylgruppe (-S(=0)-) an das Gerüst gebunden sind;Alkvisulfoxyl; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via a sulfoxyl group (-S (= 0) -);
AIVylapinocarbonyl: Alkylaminogruppen mit 1 bis 6 Kohlenstoff- atomen wie vorstehend genannt, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind;AIVylapinocarbonyl: alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the structure via a carbonyl group (-CO-);
Dialkylaminocarbonyl; Dialkylaminogruppen mit jeweils 1 bisDialkylaminocarbonyl; Dialkylamino groups each with 1 to
6 Kohlenstoffatomen pro Alkylrest wie vorstehend genannt, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind;6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
-vi \eγ}aminothiocarbonyl; Alkylaminogruppen mit 1 bis 6 Kohlen¬ stoffatomen wie vorstehend genannt, welche über eine Thio- carbonylgruppe (-CS-) an das Gerüst gebunden sind;-vi \ eγ} aminothiocarbonyl; Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
Figure imgf000024_0001
Dialkylaminogruppen mit jeweils 1 bis 6 Kohlenstoffatomen pro Alkylrest wie vorstehend genannt, welche über eine Thiocarbonylgruppe (-CS-) an das Gerüst gebunden sind;
Figure imgf000024_0001
Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
Halogenalkyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, wobei in diesen Gruppen teilweise oder voll- ständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können, z.B. Cι-C2-Halogenalkyl wie Chlor- methyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluor¬ methyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Fluorethyl, 2-Fluorethyl, 2,2-Difluorethyl, 2, 2, 2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluor¬ ethyl, 2, 2-Dichlor-2-fluorethyl, 2,2, 2-Trichlorethyl und Penta- fluorethyl;Haloalkyl; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluor¬ methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluor¬ ethyl, 2, 2-dichloro-2-fluoroethyl, 2,2, 2-trichloroethyl and pentafluoroethyl;
Alkoxy; geradkettige oder verzweigte Alkylgruppen mit 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt, welche über ein Sauerstoffatom (-0-) an das Gerüst gebunden sind, z.B. Cι-C6-Alkoxy wie Methyloxy, Ethyloxy, Propyloxy, 1-Methylethyloxy, Butyloxy, 1-Methyl-propyloxy, 2-Methylpropyloxy, 1, 1-Dimethyl- ethyloxy, Pentyloxy, 1-Methylbutyloxy, 2-Methylbutyloxy, 3-Methylbutyloxy, 2,2-Di-methylpropyloxy, 1-Ethylpropyloxy, Hexyloxy, 1, 1-Dimethylpropyloxy, 1, 2-Dimethylpropyloxy, 1-Methyl- pentyloxy, 2-Methylpentyloxy, 3-Methylpentyloxy, 4-Methylpentyl- oxy, 1, 1-Dimethylbutyloxy, 1,2-Dimethylbutyloxy, 1,3-Dimethyl- butyloxy, 2,2-Dimethylbutyloxy, 2, 3-Dimethylbutyloxy, 3, 3-Dimethylbutyloxy, 1-Ethyl-butyloxy, 2-Ethylbutyloxy, 1, 1, 2-Trimethylpropyloxy, 1, 2, 2-Trimethylpropyloxy, 1-Ethyl-l-methylpropyloxy und l-Ethyl-2-methylpropyloxy;Alkoxy; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-0-), for example C 1 -C 6 -alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, Butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy, 1, 1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy, 2,2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1, 1-dimethylpropyloxy, 1, 2-dimethylpropyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1, 1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2, 3-dimethylbutyloxy, 3, 3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1, 1, 2-trimethylpropyloxy, 1, 2, 2-trimethylpropyloxy, 1-ethyl-l- methylpropyloxy and l-ethyl-2-methylpropyloxy;
Alkoxycarbonyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, welche über eine Oxycarbonylgruppe (-OC(=0)-) an das Gerüst gebunden sind;Alkoxycarbonyl; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via an oxycarbonyl group (-OC (= 0) -);
Halogenalkoxy; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können, und wobei diese Gruppen über ein Sauerstoffatom an das Gerüst gebunden sind;Haloalkoxy; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the skeleton via an oxygen atom;
Alkylthio; geradkettige oder verzweigte Alkylgruppen mit 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt, welche über ein Schwefelatom (-S-) an das Gerüst gebunden sind, z.B. Cx-Cβ-Alkylthio wie Methylthio, Ethylthio, Propylthio, 1-Methyl- ethylthio, Butylthio, 1-Methylpropylthio, 2-Methylpropylthio, 1, 1-Dimethylethylthio, Pentylthio, 1-Methylbutylthio, 2-Methyl- butylthio, 3-Methylbutylthio, 2,2-Di-methylpropylthio, 1-Ethyl- propylthio, Hexylthio, 1, 1-Dimethylpropylthio, 1, 2-Dirnethyl- propylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methyl- pentylthio, 4-Methylpentylthio, 1,1-Dimethylbutylthio, 1,2-Dimethylbutylthio, 1,3-Dimethylbutylthio, 2, 2-Dimethylbutyl- thio, 2, 3-Dimethylbutylthio, 3,3-Dimethylbutylthio, 1-Ethylbutyl- thio, 2-Ethylbutylthio, 1, 1,2-Trimethylpropylthio, 1,2,2-Tri- methylpropylthio, 1-Ethyl-l-methylpropylthio und l-Ethyl-2-methylpropylthio;Alkylthio; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g. Cx-Cβ-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2-dirnethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-l-methylpropylthio and l-ethyl-2-methylpropylthio;
Cycloalkyl; monocyclische Alkylgruppen mit 3 bis 6 Kohlenstoff- ringgliedern, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl;Cycloalkyl; monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Alkenyl; geradkettige oder verzweigte Alkenylgruppen mit 2 bis 6 oder 10 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z.B. C2-C6-Alkenyl wie Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-l-propenyl, 2-Methyl-l-propenyl, l-Methyl-2-propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-l-butenyl, 3-Methyl-l- butenyl, l-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2- butenyl, l-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3- butenyl, 1, 1-Dimethy1-2-propenyl, 1,2-Dimethyl-l-propenyl, 5 1, 2-Dimethyl-2-propenyl, 1-Ethyl-l-propenyl, l-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-l-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-l-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, l-Methyl-3-pentenyl,Alkenyl; straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethy1-2-propenyl, 1,2-dimethyl-l-propenyl, 5 1, 2 -Dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-l-pentenyl , 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4 -Methyl-2-pentenyl, l-methyl-3-pentenyl,
10 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1, l-Dimethyl-2-butenyl, 1, l-Di-methyl-3- butenyl, 1, 2-Dimethyl-l-butenyl, 1, 2-Dimethyl-2-butenyl, l,2-Dimethyl-3-butenyl, 1, 3-Dimethyl-l-butenyl, 1,3-Dimethyl-10 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4 -Methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, l , 2-dimethyl-3-butenyl, 1, 3-dimethyl-l-butenyl, 1,3-dimethyl
15 2-butenyl, 1, 3-Dimethyl-3-butenyl, 2, 2-Dimethyl-3-butenyl,15 2-butenyl, 1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl,
2, 3-Dimethyl-l-butenyl, 2, 3-Dimethyl-2-butenyl, 2, 3-Dimethyl- 3-butenyl, 3,3-Dimethyl-l-butenyl, 3, 3-Dimethyl-2-butenyl, 1-Ethyl-l-butenyl, l-Ethyl-2-butenyl, l-Ethyl-3-butenyl, 2-Ethyl-l-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl,2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,
20 1, 1, 2-Trimethyl-2-propenyl, 1- Ethyl-l-methyl-2-propenyl, l-Ethyl-2-methyl-l-propenyl und l-Ethyl-2-methyl-2-propenyl;20 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkenyloxy; geradkettige oder verzweigte Alkenylgruppen mit 2 bis 6 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen 25 Position, welche über ein Sauerstoffatom (-0-) an das Gerüst gebunden sind;Alkenyloxy; straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-0-);
Alkenylthio bzw. Alkenvlamino; geradkettige oder verzweigte Alkenylgruppen mit 2 bis 6 Kohlenstoffatomen und einer Doppel- 30 bindung in einer beliebigen Position, welche (Alkenylthio) über ein Schwefelatom bzw. (Alkenylamino) ein Stickstoffatom an das Gerüst gebunden sind.Alkenylthio or alkenvlamino; straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which (alkenylthio) are bonded to the skeleton via a sulfur atom or (alkenylamino) a nitrogen atom.
Alkenylcarbonyl: geradkettige oder verzweigte Alkenylgruppen mit 35 2 bis 10 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind;Alkenylcarbonyl: straight-chain or branched alkenyl groups with 35 2 to 10 carbon atoms and a double bond in any position, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkinyl; geradkettige oder verzweigte Alkinylgruppen mit 2 bis 40 10 Kohlenstoffatomen und einer Dreifachbindung in einer be¬ liebigen Position, z.B. C2-C6-Alkinyl wie Ethinyl, 2-Propinyl, 2-Butinyl, 3-Butinyl, l-Methyl-2-propinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, l-Methyl-2-butinyl, l-Methyl-3-butinyl, 2-Methyl-3-butinyl, 1, l-Dimethyl-2-propinyl, l-Ethyl-2-propinyl, 45 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, l-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, l-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-2-pentinyl, 1, l-Dimethyl-2-butinyl, 1, l-Dimethyl-3-butinyl, 1, 2-Dimethyl- 3-butinyl, 2,2-Dimethyl-3-butinyl, l-Ethyl-2-butinyl, 1-Ethyl- 3-butinyl, 2-Ethyl-3-butinyl und l-Ethyl-l-methyl-2-propinyl;Alkynyl; straight-chain or branched alkynyl groups with 2 to 40 10 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl , 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl -2-propynyl, 45 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl- 3-pentinyl, 2-methyl-4-pentinyl, 3-methyl-4-pentinyl, 4-methyl-2-pentinyl, 1, l-dimethyl-2-butynyl, 1, l-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, l-ethyl-2-butynyl, 1- Ethyl 3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl;
Alkinyloxy bzw. Alkinylthio und Alkinylamino; geradkettige oder verzweigte Alkinylgruppen mit 2 bis 6 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, welche (Alkinyloxy) über ein Sauerstoffatom bzw. (Alkinylthio) über ein Schwefelatom oder (Alkinylamino) über ein Stickstoffatom an das Gerüst gebunden sind.Alkynyloxy or alkynylthio and alkynylamino; straight-chain or branched alkynyl groups with 2 to 6 carbon atoms and a triple bond in any position, which (alkynyloxy) via an oxygen atom or (alkynylthio) via a sulfur atom or (alkynylamino) via a nitrogen atom are bonded to the skeleton.
Alkinylcarbonyl; geradkettige oder verzweigte Alkinylgruppen mit 3 bis 10 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind;Alkynylcarbonyl; straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in any position, which are bonded to the skeleton via a carbonyl group (-CO-);
Cvcloalkenvl bzw. Cvcloalkenvloxv. Cvcloalkenvlthio und Cvclo-
Figure imgf000027_0001
monocyclische Alkenylgruppen mit 3 bis 6 Kohlen¬ stoffringgliedern, welche direkt bzw. (Cycloalkenyloxy) über ein Sauerstoffatom oder (Cycloalkenylthio) ein Schwefelatom oder Cycloalkenylamino) über ein Stickstoffatom an das Gerüst gebunden sind, z.B. Cyclopropenyl, Cyclobutenyl, Cyclopentenyl oder Cyclo- hexenyl.Cvcloalkenvl or Cvcloalkenvloxv. Cvcloalkenvlthio and Cvclo-
Figure imgf000027_0001
monocyclic alkenyl groups with 3 to 6 carbon ring members which are bonded to the skeleton directly or (cycloalkenyloxy) via an oxygen atom or (cycloalkenylthio) via a nitrogen atom (cycloalkenylthio), for example cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
Cvcloalkoxy bzw. Cycloalkylthio und Cycloalkylaτn-iτ.n« mono¬ cyclische Alkenylgruppen mit 3 bis 6 Kohlenstoffringgliedern, welche (Cycloalkyloxy) über ein Sauerstoffatom oder (Cycloalkyl¬ thio) ein Schwefelatom oder (Cycloalkylamino) über ein Stick¬ stoffatom an das Gerüst gebunden sind, z.B. Cyclopropyl, Cyclo- butyl, Cyclopentyl oder Cyclohexyl;Cvcloalkoxy or Cycloalkylthio and Cycloalkylaτn-iτ.n « mono-cyclic alkenyl groups with 3 to 6 carbon ring members, which (cycloalkyloxy) via an oxygen atom or (Cycloalkyl¬ thio) a sulfur atom or (Cycloalkylamino) via a nitrogen atom are attached to the skeleton , for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
Heterocvclvl bzw. Heterocvclyloxv. Heterocyclylthio und Hetero- gYC-.Y-.Miil.PT drei- bis sechsgliedrige, gesättigte oder partiell ungesättigte mono- oder polycyclische Heterocyclen, die ein bis drei Hereroatome ausgewählt aus einer Gruppe bestehend aus Sauer¬ stoff, Stickstoff und Schwefel enthalten, und welche direkt bzw. (Heterocyclyloxy) über ein Sauerstoffatom oder (Heterocyclylthio) über ein Schwefelatom oder (Heterocyclylamino) über ein Stick¬ stoffatom an das Gerüst gebunden sind, wie z.B. 2-Tetrahydro- furanyl, Oxiranyl, 3-Tetrahydrofurany1, 2-Tetrahydrothienyl,Heterocvclvl or Heterocvclyloxv. Heterocyclylthio and HeterogYC-.Y-.Miil.PT three- to six-membered, saturated or partially unsaturated mono- or polycyclic heterocycles, which contain one to three herero atoms selected from a group consisting of oxygen, nitrogen and sulfur, and which directly or (heterocyclyloxy) via an oxygen atom or (heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a nitrogen atom, such as, for example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofurany1, 2-tetrahydrothienyl,
3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-Isoxazol- dinyl, 4-Isoxazolidinyl, 5-Isoxazolidinyl, 3-Isothiazolidinyl, 4-Isothiazolidinyl, 5-Isothiazolidinyl, 3-Pyrazolidinyl, 4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-0xazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2-Thiazolidinyl, 4-Thiazolidinyl, 5-Thia- zolidinyl, 2-Imidazolidinyl, 4-Imidazolidinyl, 1,2,4-Oxa- diazolidin-3-yl, 1, 2,4-Oxadiazolidin-5-yl, 1,2,4-Thiadiazolidin- 3-yl, 1,2, 4-Thiadiazolidin-5-yl, 1,2, 4-Triazolidin-3-yl,3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoledinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-0xazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1, 2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin 3-yl, 1,2, 4-thiadiazolidin-5-yl, 1,2, 4-triazolidin-3-yl,
1,3, 4-Oxadiazolidin-2-yl, 1, 3, 4-Thiadiazolidin-2 -yl, 1,3,4-Tri- azolidin-2 -yl, 2, 3-Dihydrofur-2-yl, 2,3-Dihydrofur-3-yl,1,3, 4-oxadiazolidin-2-yl, 1, 3, 4-thiadiazolidin-2 -yl, 1,3,4-triazolidin-2 -yl, 2, 3-dihydrofur-2-yl, 2, 3-dihydrofur-3-yl,
2, 3-Dihydro-für-4-yl, 2, 3-Dihydro-für-5-yl, 2, 5-Dihydro-fur-2-yl, 2, 5-Dihydro-fur-3-yl, 2, 3-Dihydrothien-2-yl, 2, 3 -Dihydrothien-2, 3-dihydro-for-4-yl, 2, 3-dihydro-for-5-yl, 2, 5-dihydro-fur-2-yl, 2, 5-dihydro-fur-3-yl, 2, 3-dihydrothien-2-yl, 2, 3 -dihydrothien-
3-yl, 2, 3-Dihydrothien-4-yl, 2,3-Dihydrothien-5-yl, 2,5-Dihydro- thien-2-yl, 2, 5-Dihydrothien-3-yl, 2, 3-Dihydropyrrol-2-yl, 2, 3-Dihydropyrrol-3-yl, 2, 3-Dihydropyrrol-4-yl, 2,3-Dihydro- pyrrol-5-yl, 2, 5-Dihydropyrrol-2-yl, 2, 5-Dihydropyrrol-3 -yl, 2, 3-Dihydroisoxazol-3-yl, 2, 3-Dihydroisoxazol-4-yl, 2,3-Dihydro- isoxazol-5-yl, 4, 5-Dihydroisoxazol-3-yl, 4, 5-Dihydroisoxazol- 4-yl, 4, 5-Dihydroisoxazol-5-yl, 2, 5-Dihydroisothiazol-3-yl, 2, 5-Dihydroisothiazol-4-yl, 2, 5-Dihydroisothiazol-5-yl, 2, 3-Dihydroisopyrazol-3-yl, 2, 3-Dihydroisopyrazol-4-yl, 2, 3-Dihydroisopyrazol-5-yl, 4, 5-Dihydroisopyrazol-3-yl, 4, 5-Dihydroisopyrazol-4-yl, 4, 5-Dihydroisopyrazol-5-yl, 2, 5-Dihydroisopyrazol-3-yl, 2, 5-Dihydroisopyrazol-4-yl, 2, 5-Dihydroisopyrazol-5-yl, 2, 3-Dihydrooxazol-3-yl, 2, 3-Dihydro- oxazol-4-yl, 2,3-Dihydrooxazol-5-yl, 4, 5-Dihydrooxazol-3-yl, 4, 5-Dihydrooxazol-4-yl, 4, 5-Dihydrooxazol-5-yl, 2,5-Dihydro- oxazol-3-yl, 2, 5-Dihydrooxazol-4-yl, 2, 5-Dihydrooxazol-5-yl, 2,3-Dihydrothiazol-2-yl, 2,3-Dihydrothiazol-4-yl, 2,3-Dihydro- thiazol-5-yl, 4, 5-Dihydrothiazol-2-yl, 4,5-Dihydrothiazol-4-yl, 4, 5-Dihydrothiazol-5-yl, 2,5-Dihydrothiazol-2-yl, 2,5-Dihydro- thiazol-4-yl, 2, 5-Dihydrothiazol-5-yl, 2,3-Dihydroimidazol-2-yl, 2,3-Dihydroimidazol-4-yl, 2,3-Dihydroimidazol-5-yl, 4, 5-Dihydro¬ imidazol-2-yl, 4, 5-Dihydroimidazol-4-yl, 4, 5-Dihydroimidazol- 5-yl, 2, 5-Dihydroimidazol-2-yl, 2, 5-Dihydroimidazol-4-yl, 2, 5-Dihydroimidazol-5-yl, 2-Morpholinyl, 3-Morpholinyl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 3-Tetrahydro- pyridazinyl, 4-Tetrahydropyridazinyl, 2-Tetrahydropyrimidinyl, 4-Tetrahydropyrimidinyl, 5-Tetrahydropyrimidinyl, 2-Tetrahydro- pyrazinyl, 1, 3, 5-Tetrahydrotriazin-2-yl, 1, 2, 4-Tetrahydro- triazin-3-yl, 1, 3-Dihydrooxazin-2-yl, 1, 3-Dithian-2-yl, 2-Tetra- hydropyranyl, 1,3-Dioxolan-2-yl, 3,4, 5,6-Tetrahydropyridin-2-yl, 4H-l,3-Thiazin-2-yl, 4H-3, l-Benzothiazin-2-yl, 1, l-Dioxo-2, 3,4,5- tetrahydrothien-2-yl, 2H-1,4-Benzothiazin-3-yl, 2H-1,4-Benzoxa- zin-3-yl, 1,3-Dihydrooxazin-2-yl, 1, 3-Dithian-2-yl,3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3- Dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2, 5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4, 5-dihydroisoxazol-4-yl, 4, 5-dihydroisoxazol-5-yl, 2, 5-dihydroisothiazol-3-yl, 2, 5-dihydroisothiazol-4-yl, 2, 5-dihydroisothiazol-5-yl, 2, 3-dihydroisopyrazol-3-yl, 2, 3-dihydroisopyrazol-4-yl, 2, 3-dihydroisopyrazol-5-yl, 4, 5-dihydroisopyrazol-3-yl, 4, 5-dihydroisopyrazol-4-yl, 4, 5-dihydroisopyrazol-5-yl, 2, 5-dihydroisopyrazol-3-yl, 2, 5-dihydroisopyrazol-4-yl, 2, 5-dihydroisopyrazol-5-yl, 2, 3-dihydrooxazol-3-yl, 2, 3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4, 5-dihydrooxazol-3-yl, 4, 5-dihydrooxazol-4-yl, 4, 5-dihydrooxazol-5- yl, 2,5-dihydro-oxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dih ydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydro-thiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4, 5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydro-thiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5- yl, 2, 5-dihydroimidazol-2-yl, 2, 5-dihydroimidazol-4-yl, 2, 5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4- Piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1, 3, 5-tetrahydrotriazin-2-yl-2-yl triazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6- Tetrahydropyridin-2-yl, 4H-l, 3-thiazin-2-yl, 4H-3, l-benzothiazin-2-yl, 1, l-dioxo-2, 3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H -1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl,
Arvl bzw. Aryloxy. Arvlthio. Arvlcarbonvl und Arvlsulfonvl; aromatische mono- oder polycyclische Kohlenwasserstoffreste welche direkt bzw. (Aryloxy) über ein Sauerstoffatom (-0-) oder (Arylthio) ein Schwefelatom (-S-), (Arylcarbonyl) über eine Carbonylgruppe (-C0-) oder (Arylsulfonyl) über eine Sulfonyl- gruppe (-S02-) an das Gerüst gebunden sind, z.B. Phenyl, Naphthyl und Phenanthrenyl bzw. Phenyloxy, Naphthyloxy und Phenanthrenyl- oxy und die entsprechenden Carbonyl- und Sulfonylreste,-Arvl or aryloxy. Arvlthio. Arvlcarbonvl and Arvlsulfonvl; aromatic mono- or polycyclic hydrocarbon radicals which directly or (aryloxy) via an oxygen atom (-0-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-C0-) or (arylsulfonyl) via a Sulfonyl group (-S0 2 -) are bound to the skeleton, for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals,
Figure imgf000029_0001
aromatische mono- oder polycyclische Kohlenwasser- Stoffreste, welche über ein Stickstoffatom an das Gerüst gebunden sind.
Figure imgf000029_0001
aromatic mono- or polycyclic hydrocarbon residues, which are bound to the structure via a nitrogen atom.
Hetaryl bzw. Hetaryloxy. Hetarylthio. Hetarylcarbonyl und Hetarylsulfonyl; aromatische mono- oder polycyclische Reste welche neben Kohlenstoffringgliedern zusätzlich ein bis vierHetaryl or hetaryloxy. Hetarylthio. Hetarylcarbonyl and hetarylsulfonyl; aromatic mono- or polycyclic residues which in addition to carbon ring members additionally one to four
Stickstoffatome oder ein bis drei Stickstoffatome und ein Sauer¬ stoff- oder ein Schwefelatom oder ein Sauerstoff- oder ein Schwefelatom enthalten können und welche direkt bzw. (Hetaryloxy) über ein Sauerstoffatom (-0-) oder (Hetarylthio) ein Schwefelatom (-S-), (Hetarylcarbonyl) über eine Carbonylgruppe (-CO-) oder (Hetarylsulfonyl) über eine Sulfonylgruppe (-S02-) an das Gerüst gebunden sind, z.B.Nitrogen atoms or one to three nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom can contain and which directly or (hetaryloxy) via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S- ), (Hetarylcarbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group (-S0 2 -) are bound to the skeleton, for example
5-σliedriσes Heteroaryl. enthaltend ein bis drei Stickstoff- atome: 5-Ring Heteroarylgruppen, welche neben Kohlenstoff- atomen ein bis drei Stickstoffatome als Ringglieder ent¬ halten können, z.B. 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Imidazolyl, 4-Imidazolyl, 1, 2, 4-Triazol-3-yl und 1,3,4-Triazol-2-yl;5-σliedriσes heteroaryl. containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-triazol-3-yl and 1,3,4-triazol-2- yl;
5-σl-iedriσes Heteroaryl. enthaltend ein bis vier Stickstoff- atome oder ein bis drei Stickstoffatome und ein Schwefel¬ oder Sauerstoffatom oder ein Sauerstoff oder ein Schwefel- atom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoff- atomen ein bis vier Stickstoffatome oder ein bis drei Stick¬ stoffatome und ein Schwefel- oder Sauerstoffatom oder ein Sauerstoff- oder Schwefelatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-Isoxazolyl, 4-Isoxazolyl, 5-Isoxazolyl, 3-Isothiazolyl, 4-Isothiazolyl, 5-Isothiazolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-0xazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 2-Imidazolyl, 4-Imidazolyl, 1, 2, 4-0xadiazol- 3-yl, l,2,4-Oxadiazol-5-yl, 1,2,4-Thiadiazol-3-yl, l,2,4-Thiadiazol-5-yl, 1,2,4-Triazol-3-yl,5-σl-lower heteroaryl. containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one May contain sulfur or oxygen atom or an oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-0xazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-0xadiazol- 3-yl, l, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-triazol-3- yl,
1, 3, 4-Oxadiazol-2-yl, 1,3,4-Thiadiazol-2-yl, 1, 3, 4-Triazol-2-yl;1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
benzokondensiertes 5-σliedriσes Heteroaryl. enthaltend ein bis drei Stickstoffatome oder ein Stickstoffatom und/oder ein Sauerstoff- oder Schwefelatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom oder ein Sauerstoff- oder ein Schwefelatom als Ringglieder enthalten können, und in welchen zwei benachbarte Kohlenstoffringglieder oder ein Stickstoff- und ein benach- bartes Kohlenstoffringglied durch eine Buta-1, 3-dien-l, 4- diylgruppe verbrückt sein können;benzo-fused 5-σliedriσes heteroaryl. containing one to three nitrogen atoms or one nitrogen atom and / or one oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or can contain one to three nitrogen atoms and a sulfur or oxygen atom or an oxygen or a sulfur atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member by a buta-1, 3-diene-l , 4-diyl group can be bridged;
über Stickstoff gebundenes 5-σliedriσes Heteroaryl. ent¬ haltend ein bis vier stickstoffatome. oder über Stickstoff gebundenes benzokondensiertes 5-σliedriαes Heteroaryl. ent¬ haltend ein bis drei Stickstoffatome: 5-Ring Heteroaryl¬ gruppen, welche neben Kohlenstoffatomen ein bis vier Stick¬ stoffatome bzw. ein bis drei Stickstoffatome als Ringglieder enthalten können, und in welchen zwei benachbarte Kohlen- Stoffringglieder oder ein Stickstoff- und ein benachbartes5-σliedriσes heteroaryl bound via nitrogen. containing one to four nitrogen atoms. or benzo-fused 5-σliedriαes heteroaryl bound via nitrogen. containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent one
Kohlenstoffringglied durch eine Buta-1, 3-dien- 1,4-diylgruppe verbrückt sein können, wobei diese Ringe über eines der Stickstoffringglieder an das Gerüst gebunden sind;Carbon ring member can be bridged by a buta-1, 3-diene-1,4-diyl group, these rings being bonded to the framework via one of the nitrogen ring members;
- 6-gliedriαes Heteroaryl. enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoff- atome als Ringglieder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl, 2-Pyrazinyl, 1, 3, 5-Triazin-2-yl, 1,2, 4-Triazin-3-yl und 1,2,4, 5-Tetrazin-3-yl;- 6-membered heteroaryl. containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazin-2-yl, 1, 2, 4-triazin-3-yl and 1,2,4, 5-tetrazin-3-yl;
benzokondensiertes 6-gliedriges Heteroaryl. enthaltend ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen in welchen zwei benachbarte Kohlenstoffringglieder durch eine Buta-1,3-dien-1,4-diylgruppe verbrückt sein können, z.B. Chinolin, Isochinolin, Chinazolin und Chinoxalin,benzo-fused 6-membered heteroaryl. containing one to four nitrogen atoms: 6-ring heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline,
bzw. die entsprechenden Oxy-, Thio-, Carbonyl- oder Sulfonyl- gruppen.or the corresponding oxy, thio, carbonyl or sulfonyl groups.
Hetaryl»ττιιη<?T aromatische mono- oder polycyclische Reste, welche neben Kohlenstoffringgliedern zusätzlich ein bis vier Stickstoff- atome oder ein bis drei Stickstoffatome und ein Sauerstoff- oder ein Schwefelatom enthalten können und welche über ein Stickstoff- atom an das Gerüst gebunden sind.Hetaryl »ττιιη <? T aromatic mono- or polycyclic radicals, which in addition to carbon ring members can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are bonded to the structure via a nitrogen atom.
Die Angabe "partiell oder vollständig halogeniert" soll zum Aus- druck bringen, daß in den derart charakterisierten Gruppen die Wasserstoffatome zum Teil oder vollständig durch gleiche oder verschiedene Halogenatome wie vorstehend genannt ersetzt sein können.The expression "partially or completely halogenated" is intended to express that in the groups characterized in this way the hydrogen atoms are partially or completely replaced by the same or various halogen atoms as mentioned above can be replaced.
Im Hinblick auf ihre biologische Wirkung sind Verbindungen der Formel I bevorzugt, in denen m für 0 oder 1, insbesondere 0, steht.With regard to their biological action, preference is given to compounds of the formula I in which m represents 0 or 1, in particular 0.
Für den Fall, daß m für 1 steht werden Verbindungen I bevorzugt, in denen R für Chlor oder Fluor steht.In the event that m is 1, preference is given to compounds I in which R is chlorine or fluorine.
Besonders werden Verbindungen I bevorzugt, in denen X für NOCH3 (Formel 1.1) steht.Compounds I in which X is NOCH 3 (formula 1.1) are particularly preferred.
Außerdem werden Verbindungen I bevorzugt, in denen X für CHCH3 (Formel 1.2) steht.In addition, compounds I are preferred in which X represents CHCH3 (formula 1.2).
Gleichermaßen werden Verbindungen I bevorzugt, in denen X für CHOCH3 (Formel 1.3) steht.Likewise preferred are compounds I in which X is CHOCH 3 (formula 1.3).
Daneben werden Verbindungen I besonders bevorzugt, in denen R1 für Methyl steht.In addition, compounds I are particularly preferred in which R 1 is methyl.
Desweiteren werden Verbindungen I bevorzugt, in denen Y für Sau¬ erstoff steht (Formel IA) .Furthermore, compounds I are preferred in which Y represents oxygen (formula IA).
Gleichermaßen werden Verbindungen I bevorzugt, in denen Y für NR' , insbesondere NH, steht (Formel IB) .Likewise, preference is given to compounds I in which Y is NR ', in particular NH (formula IB).
Außerdem werden Verbindungen I besonders bevorzugt, in denen R2 für Cι~C4-Alkyl, insbesondere Methyl, steht.In addition, compounds I are particularly preferred in which R 2 is C 1 -C 4 -alkyl, in particular methyl.
Gleichermaßen besonders bevorzugt sind Verbindungen I, in denen R2 für Trifluormethyl steht.Likewise, particular preference is given to compounds I in which R 2 represents trifluoromethyl.
Daneben werden Verbindungen I besonders bevorzugt, in denen R2 für Cyclopropyl steht.In addition, compounds I are particularly preferred in which R 2 is cyclopropyl.
Desweiteren werden Verbindungen I besonders bevorzugt, in denen R2 für Cι-C4-Alkoxy, insbesondere Methoxy, steht.Furthermore, compounds I are particularly preferred in which R 2 is C 1 -C 4 alkoxy, in particular methoxy.
Außerdem werden Verbindungen I besonders bevorzugt, in denen R2 für Halogen, insbesondere Chlor, steht.In addition, compounds I are particularly preferred in which R 2 represents halogen, in particular chlorine.
Insbesondere werden auch Verbindungen I bevorzugt, in denen R3 für Aryl, insbesondere ggf. subst. Phenyl, steht. Außerdem werden Verbindungen I besonders bevorzugt, in denen R3 für Alkyl, insbesondere Ci-Cδ-Alkyl, steht.In particular, compounds I are also preferred in which R 3 is aryl, in particular, if appropriate, subst. Phenyl. Additionally, compounds I are particularly preferred, in which R 3 is alkyl, especially Ci-C δ -alkyl stands.
Gleichermaßen besonders bevorzugt sind Verbindungen I, in denen R3 für Alkoxy, insbesondere Ci-Cβ-Alkoxy, steht.Likewise, particular preference is given to compounds I in which R 3 represents alkoxy, in particular Ci-Cβ-alkoxy.
Daneben werden Verbindungen I besonders bevorzugt, in denen R3 für Cycloalkyl, insbesondere C3-C6~Cycloalkyl, steht.In addition, compounds I are particularly preferred in which R 3 is cycloalkyl, in particular C 3 -C 6 ~ cycloalkyl.
Desweiteren werden Verbindungen I besonders bevorzugt, in denen R3 für Aryloxyalkyl, insbesondere im Phenylteil ggf. subst. Phenoxy- Cι-C2-alkyl, steht.Furthermore, compounds I are particularly preferred in which R 3 for aryloxyalkyl, in particular in the phenyl part, if appropriate, subst. Phenoxy -C-C 2 alkyl, is.
Außerdem werden Verbindungen I besonders bevorzugt, in denen R3 für Hetaryl, insbesondere ggf. subst. Thienyl, Isoxazolyl, Pyra¬ zolyl und Pyridinyl, steht.In addition, compounds I are particularly preferred in which R 3 is hetaryl, in particular, if appropriate, subst. Thienyl, isoxazolyl, pyrazolyl and pyridinyl.
Insbesondere werden auch Verbindungen I bevorzugt, in denen R4 für Ci-Cβ-Alkyl, insbesondere Methyl, steht.Compounds I in which R 4 is C 1 -C 6 -alkyl, in particular methyl, are also particularly preferred.
Außerdem werden Verbindungen I besonders bevorzugt, in denen R4 für C3-C6-Alkenyl, insbesondere Allyl, steht.In addition, compounds I are particularly preferred in which R 4 is C 3 -C 6 alkenyl, in particular allyl.
Gleichermaßen besonders bevorzugt sind Verbindungen I, in denen R4 für C3-C6-Alkinyl, insbesondere Propargyl steht.Likewise, particular preference is given to compounds I in which R 4 is C 3 -C 6 -alkynyl, in particular propargyl.
Daneben werden Verbindungen I besonders bevorzugt, in denen R4 für Arylalkyl, insbesondere im Phenylteil ggf. subst. Phenyl-Cι~C2-al- kyl, steht.In addition, compounds I are particularly preferred in which R 4 for arylalkyl, in particular in the phenyl part, if appropriate, subst. Phenyl-C ~ C 2 alkyl, stands.
Desweiteren werden Verbindungen I besonders bevorzugt, in denen R4 für Haloalkenyl, insbesondere trans-Chlorallyl, steht.Furthermore, compounds I are particularly preferred in which R 4 represents haloalkenyl, in particular trans-chloroallyl.
Außerdem werden Verbindungen I besonders bevorzugt, in denen R4 für Alkoxyalkyl, insbesondere Cι-C2-Alkoxy-Cι-C2-alkyl, steht.In addition, compounds I are particularly preferred in which R 4 is alkoxyalkyl, in particular C 1 -C 2 alkoxy-C 1 -C 2 alkyl.
Insbesondere werden Verbindungen I bevorzugt, in denen der Rest CfsOO-COYR1 in 2-Position des Pyridylrings gebunden ist.In particular, compounds I are preferred in which the CfsOO-COYR 1 radical is bonded in the 2-position of the pyridyl ring.
Daneben werden Verbindungen I bevorzugt, in denen der Rest C(=X)-C0YR1 in 3-Position des Pyridylrings gebunden ist.In addition, compounds I are preferred in which the radical C (= X) -C0YR 1 is bonded in the 3-position of the pyridyl ring.
Außerdem werden Verbindungen I bevorzugt, in denen der Rest C(=X)-C0YR1 in 4-Position des Pyridylrings gebunden ist. Insbesondere werden auch Verbindungen I bevorzugt, in denen der Rest -CH2ON=CR2-CR3=NOR4 in 2-Position des Pyridylrings gebunden ist.In addition, compounds I are preferred in which the radical C (= X) -C0YR 1 is bonded in the 4-position of the pyridyl ring. In particular, compounds I are also preferred in which the radical -CH 2 ON = CR 2 -CR 3 = NOR 4 is bonded in the 2-position of the pyridyl ring.
Daneben werden Verbindungen I bevorzugt, in denen der Rest - CH2ON=CR2-CR3=NOR4 in 3-Position des Pyridylrings gebunden ist.In addition, compounds I are preferred in which the radical —CH 2 ON = CR 2 —CR 3 = NOR 4 is bonded in the 3-position of the pyridyl ring.
Außerdem werden Verbindungen I bevorzugt, in denen der Rest - CH2ON=CR2-CR3=NOR4 in 4-Position des Pyridylrings gebunden ist.In addition, compounds I are preferred in which the radical - CH 2 ON = CR 2 -CR 3 = NOR 4 is bonded in the 4-position of the pyridyl ring.
Insbesondere werden Verbindungen I bevorzugt, in denen der Rest C(=X)-COYR1 in 3-Position und der Rest -CH2ON=CR2-CR3=NOR4 in 2-Position des Pyridylrings gebunden ist.Compounds I are particularly preferred in which the radical C (= X) -COYR 1 is bonded in the 3-position and the radical -CH 2 ON = CR 2 -CR 3 = NOR 4 in the 2-position of the pyridyl ring.
Tabelle 1Table 1
Verbindungen der allgemeinen Formel IA . l , in denen die Kombina ¬ tion der Substi tuenten R2 , R3 und R4 für eine Verbindung j eweils einer Zeile der Tabelle A entsprichtCompounds of the general formula IA. l, in which the combination of the substituents R 2 , R 3 and R 4 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0001
C02CH3 Tabelle 2
Figure imgf000033_0001
C0 2 CH 3 Table 2
Verbindungen der allgemeinen Formel IA.2, in denen die Kombina¬ tion der Substituenten R2, R3 und R4 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the general formula IA.2, in which the combination of the substituents R 2 , R 3 and R 4 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0002
C02CH3 Tabelle 3
Figure imgf000033_0002
C0 2 CH 3 Table 3
Verbindungen der allgemeinen Formel IA.3, in denen die Kombina¬ tion der Substituenten R2, R3 und R4 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the general formula IA.3, in which the combination of the substituents R 2 , R 3 and R 4 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0003
Figure imgf000033_0003
C02CH3 Tabelle 4C0 2 CH 3 Table 4
Verbindungen der allgemeinen Formel IA.3, in denen die Kombina¬ tion der Substituenten R2, R3 und R4 für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the general formula IA.3, in which the combination of the substituents R 2 , R 3 and R 4 for a compound corresponds in each case to one line of Table A.
Figure imgf000034_0001
CONHCH3
Figure imgf000034_0001
CONHCH 3
Tabelle ATable A
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Tabelle I :
Figure imgf000123_0001
Table I:
Ausgewählte physikal . Daten einiger VerbindungenSelected phys. Some connections data
00
5
Figure imgf000124_0001
physikal. Daten: Fp [°C]5
Figure imgf000124_0001
phys. Data: Fp [° C]
IR [cm'1] oder 0 iH-NMR [ppm]IR [cm ' 1 ] or 0 i H-NMR [ppm]
Die Verbindungen I eignen sich als Fungizide.The compounds I are suitable as fungicides.
Die Verbindungen I zeichnen sich durch eine hervorragende Wirk- -> samkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten und Basidiomyceten, aus. Sie sind zum Teil systemisch wirksam und können als Blatt- und Bodenfungizide eingesetzt werden. 0 Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Baumwolle, Soja, Kaffee, Zucker¬ rohr, Wein, Obst- und Zierpflanzen und Gemüsepflanzen wie Gurken, Bohnen und Kürbisgewächsen, sowie an den Samen dieser Pflanzen. 5The compounds I are distinguished by an excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers , Beans and pumpkin plants, as well as on the seeds of these plants. 5
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrank¬ heiten: Erysiphe graminis (echter Mehltau) in Getreide, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Podosphaera leucotricha an Äpfeln, üncinula necator an Reben, 0 Puccinia-Arten an Getreide, Rhizoctonia-Arten an Baumwolle und Rasen, Ustilago-Arten an Getreide und Zuckerrohr, Venturia inaequalis (Schorf) an Äpfeln, Helminthosporium-Arten an Getreide, Septoria nodorum an Weizen, Botrytis cinerea (Grau¬ schimmel) an Erdbeeren, Reben, Cercospora arachidicola an Erd¬ 5 nüssen, Pseudocercosporella herpotrichoides an Weizen, Gerste, Pyricularia oryzae an Reis, Phytophthora infestans an Kartoffeln und Tomaten, Fusarium- und Verticillium-Arten an verschiedenen Pflanzen, Plasmopara viticola an Reben, Alternaria-Arten an Gemüse und Obst.They are especially suitable for combating the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, üncinula necator on vines, 0 Pucciniao species on cereals, 0 Pucciniao species on cereals and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various Plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.
Die Verbindungen I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter,The compounds I are used by the fungi or the plants, seeds,
Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung erfolgt vor oder nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze.Materials or the soil are treated with a fungicidally effective amount of the active ingredients. It is used before or after the infection of the materials, plants or seeds by the fungi.
Sie können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleich¬ mäßige Verteilung der erfindungsgemäßen Verbindungen gewährlei- sten. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgier¬ mitteln und Dispergiermitteln, wobei im Falle von Wasser als Ver¬ dünnungsmittel auch andere organische Lösungsmittel als Hilfs- lösungsmittei verwendet werden können. Als Hilfsstoffe kommen da¬ für im wesentlichen in Betracht: Lösungsmittel wie Aromaten (z.B. Xylol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol), Ketone (z.B. Cyclohexanon), Amine (z.B. Ethanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate) ; Emulgiermittel wie nicht¬ ionogene und anionische Emulgatoren (z.B. Polyoxyethylen-Fettal- kohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergier- mittel wie Lignin-Sulfitablaugen und Methylcellulose.They can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compounds according to the invention. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine) , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.% Wirkstoff.The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
Die Aufwandmengen liegen je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha.Depending on the type of effect desired, the application rates are between 0.01 and 2.0 kg of active ingredient per ha.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 0,1 g, vorzugsweise 0,01 bis 0,05 g je Kilogramm Saatgut benötigt.In the case of seed treatment, amounts of active ingredient of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
Die erfindungsgemäßen Mittel können in der Anwendungsform als Fungizide auch zusammen mit anderen Wirkstoffen vorliegen, der z.B. mit Herbiziden, Insektiziden, Wachstumsregulatoren, Fungiziden oder auch mit Düngemitteln. Beim Vermischen mit Fungiziden erhält man dabei in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums.In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.
Die folgende Liste von Fungiziden, mit denen die erfindungs- gemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken:The following list of fungicides with which the compounds according to the invention can be used together is intended to explain the possible combinations, but not to limit it:
Schwefel, Dithiocarbamate und deren Derivate, wie Ferridimethyl- dithiocarbamat, Zinkdimethyldithiocarbamat, Zinkethylenbisdithio- carbamat, Manganethylenbisdithiocarbamat, Mangan-Zink-ethylen- diamin-bis-dithiocarbamat, Tetramethylthiuramdisulfide, Ammoniak- Komplex von Zink- (N,N-ethylen-bis-dithiocarbamat) , Ammoniak- Komplex von Zink-(N,N' -propylen-bis-dithiocarbamat) , Zink-(N,N'- propylenbis-dithiocarbamat) , N,N'-Polypropylen-bis- (thiocarba- moyl-disulfid;Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylene diamine bis-dithiocarbamate, tetramethylthiurium dibiammamodisulfide ), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl disulfide;
Nitroderivate, wie Dinitro- (1-methylheptyl) -phenylcrotonat, 2-sec-Butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylat, 2-sec-Butyl- 4, 6-dinitrophenyl-isopropylcarbonat, 5-Nitro-isophthalsäure- di-isopropylester;Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalic acid - di-isopropyl ester;
heterocyclische Substanzen, wie 2-Heptadecyl-2-imidazolin-acetat, 2, 4-Dichlor-6- (o-chloranilino)-s-triazin, O,O-Diethyl-phthal- imidophosphonothioat, 5-Amino-l- [bis- (dimethylamino) -phosphi- nyl] -3-phenyl-l, 2, 4- triazol, 2,3-Dicyano-l, 4-dithioanthrachinon, 2-Thio-l,3-dithiolo[4, 5-b] chinoxalin, 1- (Butylcarbamoyl) -2-benz- imidazol-carbaminsäuremethylester, 2-Methoxycarbonylamino-benz- imidazol, 2- (Furyl-(2) )-benzimidazol, 2- (Thiazolyl- (4) )-benz- imidazol, N- (1, 1,2,2-Tetrachlorethylthio)-tetrahydrophthalimid, N-Trichlormethylthio-tetrahydrophthalimid, N-Trichlormethylthio- phthalimid,heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) phosphinyl] -3-phenyl-l, 2, 4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,
N-Dichlorfluormethylthio-N' ,N'-dimethyl-N-phenyl-schwefelsäure- diamid, 5-Ethoxy-3-trichlormethyl-l, 2, 3-thiadiazol, 2-Rhodan- methylthiobenzthiazol, 1, 4-Dichlor-2, 5-dimethoxybenzol,N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 1,4-dichloro-2, 5-dimethoxybenzene,
4- (2-Chlorphenylhydrazono) -3-methyl-5-isoxazolon, Pyridin-2-thio- 1-oxid, 8-Hydroxychinolin bzw. dessen Kupfersalz, 2,3-Dihydro-5- carboxanilido-6-methyl-l,4-oxathiin, 2, 3-Dihydro-5-carboxanilido- 6-methyl-l,4-oxathiin-4, 4-dioxid, 2-Methyl-5,6-dihydro-4H-pyran- 3-carbonsäure-anilid, 2-Methyl-furan-3-carbonsäureanilid,4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin, 2, 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide,
2, 5-Dimethyl-furan-3-carbonsäureanilid, 2,4, 5-Trimethyl-furan-3- carbonsäureanilid, 2, 5-Dimethyl-furan-3-carbonsäurecyclohexyl- amid, N-Cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carbonsäure- amid, 2-Methyl-benzoesäure-anilid, 2-Iod-benzoesäure-anilid, N-Formyl-N-morpholin-2,2,2-trichlorethylacetal, Piperazin-1, 4- diylbis- (1- (2,2, 2-trichlor-ethyl)-formamid, 1- (3, 4-Dichlor- anilino) -l-formylamino-2,2,2-trichlorethan, 2, 6-Dimethyl-N-tri- decyl-morpholin bzw. dessen Salze, 2,6-Diπ.ethyl-N-cyclododecyl- morpholin bzw. dessen Salze, N-[3-(p-tert.-Butylphenyl)-2-methyl- propyl] -cis-2,6-dimethyl-morpholin, N-[3- (p-tert.-Butylphenyl)-2- methylpropyl] -piperidin, 1- [2- (2,4-Dichlorphenyl)-4-ethyl-l, 3- dioxolan-2-yl-ethyl]-lH-l,2,4-triazol, 1- [2- (2,4-Dichlorphenyl)- 4-n-propyl-l,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazol, N- (n-Propyl)-N- (2,4,6-trichlorphenoxyethyl)-N' -imidazol-yl- harnstoff, 1- (4-Chlorphenoxy)-3, 3-dimethyl-l- (1H-1,2,4-triazol- 1-yl) -2-butanon, 1- (4-Chlorphenoxy)-3, 3-dimethyl-l- (1H-1,2, 4- triazol-l-yl)-2-butanol, α- (2-Chlorphenyl)-α- (4-chlorphenyl)-5- pyrimidin-methanol, 5-Butyl-2-dirnethylamino-4-hydroxy-6-methyl- pyrimidin, Bis- (p-chlorphenyl)-3-pyridinmethanol, l,2-Bis-(3- ethoxycarbonyl-2-thioureido)-benzol, 1,2-Bis- (3-methoxycarbonyl- 2-thioureido) -benzol,2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid cyclohexyl amide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxylic acid amide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1, 4- diylbis- (1- (2,2, 2-trichloro-ethyl) -formamide, 1- (3, 4-dichloro-anilino) -l-formylamino-2,2,2-trichloroethane, 2, 6-dimethyl-N -tri- decyl-morpholine or its salts, 2,6-Diπ.ethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methyl-propyl] -cis-2 , 6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane -2-yl-ethyl] -lH-l, 2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-yl-ethyl] - 1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N '-imidazol-yl-urea, 1- (4-chlorophenoxy) -3, 3 -dimethyl-l- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1,2, 4- triazol-l-yl) -2-butanol, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine , Bis (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,
sowie verschiedene Fungizide, wie Dodecylguanidinacetat, 3- [3-(3,5-Dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutarimid, Hexachlorbenzol, DL-Methyl-N- (2,6-dimethyl-phenyl)-N-furoyl(2)- alaninat, DL-N- (2,6-Dimethyl-phenyl)-N- (2'-methoxyacety1)-alanin- methyl- ester, N- (2,6-Dimethylphenyl)-N-chloracetyl-D,L-2-amino- butyrolacton, DL-N- (2,6-Dimethylphenyl) -N- (phenylacetyl)-alanin- methylester, 5-Methyl-5-vinyl-3- (3, 5-dichlorphenyl) -2, 4-dioxo- 1, 3-oxazolidin, 3- [3, 5-Dichlorphenyl (-5-methyl-5-methoxymethyl] - 1,3-oxazolidin- 2,4-dion, 3- (3, 5-Dichlorphenyl) -1-isopropylcarba- moylhydantoin, N- (3,5-Dichlorphenyl)-1, 2-dimethylcyclopropan- 1,2-dicarbonsäureimid, 2-Cyano- [N- (ethylaminocarbonyl) -2-methox- imino] -acetamid, 1-[2-(2,4-Dichlorphenyl) -pentyl] -1H-1,2,4-tri¬ azol, 2,4-Difluor-α- (1H-1,2,4-triazolyl-1-methyl)-benzhydryl- alkohol, N- (3-Chlor-2,6-dinitro-4-trifluormethyl-phenyl)-5- trifluormethyl-3-chlor-2-aminopyridin, 1- ( (bis- (4-Fluorphenyl)- methylsilyl)-methyl)-1H-1,2,4-triazol.as well as various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N -furoyl (2) - alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacety1) -alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl -D, L-2-amino-butyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5-dichlorophenyl) -2, 4-dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3,5 -Dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1, 2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] - acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1 -methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5- trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4-fluorophenyl ) - methylsilyl) -methyl) -1H-1,2,4-triazole.
Die Verbindungen der Formel I sind außerdem geeignet, Schädlinge aus der Klasse der Insekten, Spinnentiere und Nematoden wirksam zu bekämpfen. Sie können im Pflanzenschutz sowie auf dem Hygiene-, Vorratsschutz- und Veterinärsektor als Schädlings¬ bekämpfungsmittel eingesetzt werden.The compounds of the formula I are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
Zu den schädlichen Insekten gehören aus der Ordnung der Schmet- terlinge (Lepidoptera) beispielsweise Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparga- nothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensiε.From the order of the butterflies (Lepidoptera), the harmful insects include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticuluraura, chorumobistana, Cheata- riforumana, Cheimatobella, Cheimatobella occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina Leiscellaigellaa, lucellaellaella, lua pulellaella, lua pulellaella, lua pulellaella, lua pulellaella, laphyella maca , Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparga- nothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Zeichoplirasia n.
Aus der Ordnung der Käfer (Coleoptera) beispielsweise Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp. , Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Byus Bruchus pisorusum , Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornisis, Diabrotica, diabrotica, Epibrotusisinotilisisinodisinotis, Epabritus histopathy , Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema orynhiachono , Phyllophaga sp. , Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.
Aus der Ordnung der Zweiflügler (Diptera) beispielsweise Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthro- pophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.From the order of the dipterous insects (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria Contarinia sorghicola, Cordylobia, anthropogenic pophaga, Culex pipiens, Dacus cucurbitae, oleae Dacus, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cupata, Lucilia serata Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovacosa, Tipula olovacosa, Tipula olovacosa, Tipula olovacosa
Aus der Ordnung der Thripse (Thysanoptera) beispielsweise Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.From the order of the thrips (Thysanoptera), for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
Aus der Ordnung der Hautflügler (Hymenoptera) beispielsweise Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
Aus der Ordnung der Wanzen (Heteroptera) beispielsweise Acroster- num hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.From the order of the bugs (Heteroptera), for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularisis, Lygus pratidularisis, Neopara solatularisis, Pies Thyanta perditor.
Aus der Ordnung der Pflanzensauger (Homoptera) beispielsweise Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nord- mannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.From the order of the plant suckers (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypy, Dreianafiaisolumiaia, Dreianafusiaolaia, Dreianafusiaolaia, Dreyfusiaolaia Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Psorylomyidalid, Psorylomyidalid, Psorylomyidis malic, Phorodlaid mali, Psorylomidis malic, Phorodlaid mali, Phorodlais malic, Phorodlais malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malical, Psoryllaid malicum , Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.
Aus der Ordnung der Termiten (Isoptera) beispielsweise Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.
Aus der Ordnung der Geradflügler (Orthoptera) beispielsweise Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migrato- ria, Melanoplus bivittatus, Melanoplus femur-rubrum. Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.From the order of the straight wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum. Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
Aus der Klasse der Arachnoidea beispielsweise Spinnentiere (Acarina) wie Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetra- nychus urticae.From the class of the arachnoid, for example arachnids (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shedelodi, iodine eroniophus, Iotetroniiuncus, Iotetranyius, Iotetronii Ixodes rubicundus, Ornithodorus moubata Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.
Aus der Klasse der Nematoden beispielsweise Wurzelgallen- nematoden, z.B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Zysten bildende Nematoden, z.B. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, Stock- und Blattälchen, z.B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.From the class of nematodes, for example, root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stick and leaf wholes, e.g. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchususususususususususususususususususchusususususususchusatus, Pratchylenate, Prat.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden.The active substance concentrations in the ready-to-use preparations can be varied over a wide range.
Im allgemeinen liegen sie zwischen 0,0001 und 10 %, vorzugsweise zwischen 0,01 und 1 %. Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume- Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulie¬ rungen mit mehr als 95 Gew.% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
Die Aufwandmenge an Wirkstoff zur Bekämpfung von Schädlingen beträgt unter Freilandbedingungen 0,1 bis 2,0, vorzugsweise 0, 2 bis 1, 0 kg/ha.The amount of active ingredient used to control pests is 0.1 to 2.0, preferably 0.2 to 1.0, kg / ha under field conditions.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Öldispersionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Benzol, Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Chloroform, Tetrachlorkohlenstoff, Cyclo- hexanol, Cyclohexanon, Chlorbenzol, Isophoron, stark polare Lösungsmittel, z.B. Dimethylformamid, Dimethylsulfoxid, N-Methyl- pyrrolidon, Wasser, in Betracht.To produce directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsio- nen, Pasten oder Öldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsulfonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylaryl- sulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate und Fettsäuren sowie deren Alkali- und Erdalkalisalze, Salze von sulfatiertem Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfon¬ säure mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkyl- phenolpolyglykolether, TributyIphenyIpolyglykolether, Alkylaryl- polyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid- Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpolyglykolether- acetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with Formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl ipolyglycol ether, alkylaryl polyether alcoholoxy, ethoxylated ethoxylated alcohol, fatty alcohol ethoxylated alcohol - acetal, sorbitol esters, lignin sulfite liquors and methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.%, vorzugsweise zwischen 0,1 und 90 Gew.% des Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Spektrum) eingesetzt.The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Beispiele für Formulierungen sind:Examples of formulations are:
I. 5 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 5 Gew.% des Wirkstoffs enthält.I. 5 parts by weight of a compound according to the invention are intimately mixed with 95 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 5% by weight of the active ingredient.
II. 30 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit einer Mischung aus 92 Gew.-Teilen pulverförmigem Kiesel- säuregel und 8 Gew.-Teilen Paraffinöl, das auf die Ober¬ fläche dieses Kieselsäuregels gesprüht wurde, innig ver¬ mischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit (Wirkstoffgehalt 23 Gew.%) .II. 30 parts by weight of a compound according to the invention are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesiveness (active ingredient content 23% by weight) is obtained.
III. 10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 90 Gew.-Teilen Xylol, 6 Gew.- Teilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 2 Gew.-Teilen Kalzium¬ salz der Dodecylbenzolsulfonsäure und 2 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht (Wirkstoffgehalt 9 Gew.%) .III. 10 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 9% by weight).
IV. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 60 Gew.-Teilen Cyclohexanon, 30 Gew.-Teilen Isobutanol, 5 Gew.-Teilen des Anlagerungs¬ produktes von 7 Mol Ethylenoxid an 1 Mol Isooctylphenol und 5 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylen¬ oxid an 1 Mol Ricinusöl besteht (Wirkstoffgehalt 16 Gew.%) .IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 16% by weight).
V. 80 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin- alpha-sulfonsäure, 10 Gew.-Teilen des Natriumsalzes einerV. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid and 10 parts by weight of the sodium salt
Ligninsulfonsäure aus einer Sulfit-Ablauge und 7 Gew.-Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen (Wirkstoffgehalt 80 Gew.%).Lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight Powdered silica gel mixed well and ground in a hammer mill (active ingredient content 80% by weight).
VI. Man vermischt 90 Gew.-Teile einer erfindungsgemäßen Ver- bindung mit 10 Gew.-Teilen N-Methyl-α-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist (Wirkstoffgehalt 90 Gew.%) .VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops (active substance content 90% by weight).
VII. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 40 Gew.-Teilen Cyclohexanon,VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,
30 Gew.-Teilen Isobutanol, 20 Gew.-Teilen des Anlagerungs¬ produktes von 7 Mol Ethylenoxid an 1 Mol Isooctylphenol und 10 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylen¬ oxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gew.-Teilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.% des Wirkstoffs enthält.30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
VIII.20 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin-α- sulfonsäure, 17 Gew.-Teilen des Natriumsalzes einer Lignin¬ sulfonsäure aus einer Sulfit-Ablauge und 60 Gew.-Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20 000 Gew.-Teilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.% des Wirkstoffs enthält.VIII.20 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogen¬ granulate, können durch Bindung der Wirkstoffe an feste Träger- Stoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineral- erden, wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Kalzium- und Magnesiumsulfat, Magnesium¬ oxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammonium- sulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanz¬ liche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nuß- schalenmehl, Cellulosepulver und andere feste Trägerstoffe.Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
Zu den Wirkstoffen können Öle verschiedenen Typs, Herbizide, Fungizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix) , zugesetzt werden. Diese Mittel können zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1:10 bis 10:1 zugemischt werden. SynthesebeispieleOils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1. Synthesis examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Ausgangs- Verbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in den anschließenden Tabellen mit physikalischen Angaben aufgeführt.The instructions given in the synthesis examples below were used with the appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the tables below with physical details.
1. Synthese von1. Synthesis of
Figure imgf000134_0001
Figure imgf000134_0001
a) 2-Methyl-3-formylpyridin-cyanhydrina) 2-methyl-3-formylpyridine-cyanohydrin
Eine Mischung von 33 g (0,5 Mol) KCN und 26 g (0,5 MolA mixture of 33 g (0.5 mol) of KCN and 26 g (0.5 mol
NH4C1 in 200 ml Wasser und 30 g (0,24 Mol)NH 4 C1 in 200 ml water and 30 g (0.24 mol)
2-Methyl-3-formylpyridin (Chem. Pharm. Bull. 42 (1994), 1941; J. Med. Chem. 3_2 (1989), 583; J. Heterocycl.2-methyl-3-formylpyridine (Chem. Pharm. Bull. 42 (1994), 1941; J. Med. Chem. 3_2 (1989), 583; J. Heterocycl.
Chem. 2Ä (1991), 1315; J. Org. Chem. 42 (1978), 324) in 200 ml Diethylether wird 2 Stunden bei Raumtemperatur ge¬ rührt, wobei das Produkt auskristallisiert. Der Festkör¬ per wird abgesaugt, mit Methyl-t-butylether gewaschen und im Stickstoffström getrocknet (Ausbeute: 19,3 g (54 %) ; Fp = 139°C) .Chem. 2A (1991), 1315; J. Org. Chem. 42 (1978), 324) in 200 ml of diethyl ether is stirred for 2 hours at room temperature, the product crystallizing out. The solid is filtered off with suction, washed with methyl t-butyl ether and dried in a stream of nitrogen (yield: 19.3 g (54%); mp = 139 ° C.).
iH-NMR (DMS0-d6; δ in ppm): i H-NMR (DMS0-d 6 ; δ in ppm):
8,5 (d, breit, IH, Pyridyl); 7,9 (d, breit, IH, Pyridyl); 7,3 (dd, IH, Pyridyl; 7,2 (s, breit, IH, OH); 5,9 (s, IH, CH) ; 2,55 (s, 3H, CH3) .8.5 (d, broad, IH, pyridyl); 7.9 (d, broad, IH, pyridyl); 7.3 (dd, IH, pyridyl; 7.2 (s, broad, IH, OH); 5.9 (s, IH, CH); 2.55 (s, 3H, CH 3 ).
b) (2-Methylpyridyl-3) -α-hydroxy-essigsäuremethylesterb) (2-Methylpyridyl-3) -α-hydroxy-acetic acid methyl ester
In eine Lösung von 22 g (0,15 Mol) 2-Methyl-3-formylpyri- din-cyanhydrin (Beispiel la) in 250 ml Methanol werden 15 g (0,4 Mol) gasförmige Salzsäure eingeleitet. Man rührt die Reaktionsmischung über Nacht bei Raumtemperatur und dampft anschließend im Vakuum ein. Der Rückstand wird in 200 ml Wasser aufgenommen und 1 Stunde zum Rückfluß erhitzt. Anschließend wird die Reaktionsmischung auf Raumtemperatur abgekühlt, mit NaHC03-Lösung neutralisiert und mit Methylenchlorid extrahiert. Die vereinigten orga¬ nischen Phasen werden über MgS04 getrocknet und einge¬ engt. Der Rückstand wird säulenchromatographisch mit Cy- clohexan/Essigester-Gemischen gereinigt. Man erhält 3,0 g (11 %) der TitelVerbindung als helles Öl.15 g (0.4 mol) of gaseous hydrochloric acid are introduced into a solution of 22 g (0.15 mol) of 2-methyl-3-formylpyridine-cyanohydrin (Example la) in 250 ml of methanol. The reaction mixture is stirred at room temperature overnight and then evaporated in vacuo. The residue is taken up in 200 ml of water and heated to reflux for 1 hour. The reaction mixture is then cooled to room temperature, neutralized with NaHC0 3 solution and extracted with methylene chloride. The combined organic phases are dried over MgSO 4 and concentrated. The residue is purified by column chromatography using cyclohexane / ethyl acetate mixtures. 3.0 g (11%) of the title compound are obtained as a pale oil.
i-H-NMR (CDC13; δ in ppm): i -H-NMR (CDC1 3 ; δ in ppm):
8,35 (d, breit, IH, Pyridyl); 7,7 (d, breit, IH, Pyridyl); 7,15 (dd, IH, Pyridyl); 5,4 (s, IH, CH) ; 4,5 (s, sehr breit, IH, OH); 3,75 (s, 3H, OCH3) ; 2,6 (s, 3H,8.35 (d, broad, IH, pyridyl); 7.7 (d, broad, IH, pyridyl); 7.15 (dd, IH, pyridyl); 5.4 (s, IH, CH); 4.5 (s, very broad, IH, OH); 3.75 (s, 3H, OCH 3 ); 2.6 (s, 3H,
CH3) .CH 3 ).
c) (2-Methylpyridyl-3) -glyoxylsäuremethylesterc) (2-Methylpyridyl-3) glyoxylic acid methyl ester
Eine gerührte Mischung von 3 g (16 mmol) (2-Methyl- pyridyl-3) -α-hydroxy-essigsäuremethylester (Beispiel lb) in 20 ml Methylenchlorid und 0,5 g (3,5 mmol) Na2HP04, 0,6 g (5 mmol) NaH2P04 und 0,2 g (1,6 mmol) KBr in 20 ml Wasser wird mit einer Spatelspitze Tetramethylpyridin- N-oxyl und 10 ml 12,5 %iger Na-Hypochlorit-Lösung ver¬ setzt. Man rührt 1 Stunde bei Raumtemperatur, trennt an¬ schließend die organische Phase ab und engt sie ein. Als Rückstand erhält man 2,2 g (77 %) der TitelVerbindung als gelbes Öl.A stirred mixture of 3 g (16 mmol) (2-methyl-3-pyridyl) -α-hydroxy-methyl acetate (Example lb) in 20 ml of methylene chloride and 0.5 g (3.5 mmol) of Na 2 HP0 4, 0 , 6 g (5 mmol) of NaH 2 PO 4 and 0.2 g (1.6 mmol) of KBr in 20 ml of water are mixed with a spatula tip of tetramethylpyridine-N-oxyl and 10 ml of 12.5% Na hypochlorite solution ¬ sets. The mixture is stirred for 1 hour at room temperature, then the organic phase is separated off and concentrated. 2.2 g (77%) of the title compound are obtained as a residue as a yellow oil.
iH-NMR (CDC13; δ in ppm):iH-NMR (CDC1 3 ; δ in ppm):
8,7 (d, breit, IH, Pyridyl), 8,05 (d, breit, IH, Pyridyl); 7,3 (dd, IH, Pyridyl); 4,0 (s, 3H, OCH3) ; 2,8 (s, 3H, CH3) .8.7 (d, broad, IH, pyridyl), 8.75 (d, broad, IH, pyridyl); 7.3 (dd, IH, pyridyl); 4.0 (s, 3H, OCH 3 ); 2.8 (s, 3H, CH 3).
d) (2-Methylpyridyl-3) -glyoxylsäuremethylester-trans-O-me- thyloximd) (2-methylpyridyl-3) -glyoxylsäuremethylester-trans-O-methyloxime
Eine Mischung von 2,2 g (12 mmol) (2-Methyl- pyridyl-3) -glyoxylsäuremethylester (Beispiel lc) und 1,5 g (18 mmol) o-Methylhydroxylamin-hydrochlorid in 20 ml Methanol wird über Nacht bei Raumtemperatur ge¬ rührt. Anschließend wird die Reaktionsmischung eingeengt. Der Rückstand wird in Methylenchlorid aufgenommen und mit wenig Wasser extrahiert. Die organische Phase wird über MgS04 getrocknet und eingeengt. Der Rückstand wird säulenchromatographisch mit Cyclohexan-Essigester-Gemi¬ schen gereinigt. Man erhält 1,8 g (73 %) der Titel¬ verbindung als helles Öl. iH -NMR (CDC13 , δ in ppm ) :A mixture of 2.2 g (12 mmol) (2-methyl-pyridyl-3) -glyoxylsäuremethylester (Example lc) and 1.5 g (18 mmol) of o-methylhydroxylamine hydrochloride in 20 ml of methanol is ge overnight at room temperature ¬ stirs. The reaction mixture is then concentrated. The residue is taken up in methylene chloride and extracted with a little water. The organic phase is dried over MgS0 4 and concentrated. The residue is purified by column chromatography using cyclohexane / ethyl acetate mixtures. 1.8 g (73%) of the title compound are obtained as a pale oil. iH -NMR (CDC1 3 , δ in ppm):
8,55 (d, breit, IH, Pyridyl); 7,45 (d, breit, IH, Pyridyl), 7,2 (dd, IH, Pyridyl); 4,1 (s, 3H, OCH3) ; 3,9 (s, 3H, OCH3); 2,45 (s, 3H, CH3) .8.55 (d, broad, IH, pyridyl); 7.45 (d, broad, IH, pyridyl), 7.2 (dd, IH, pyridyl); 4.1 (s, 3H, OCH 3 ); 3.9 (s, 3H, OCH 3 ); 2.45 (s, 3H, CH 3).
e) (2-Brommethylpyridyl-3) -glyoxylsäuremethylester-trans- O-methyloxime) (2-bromomethylpyridyl-3) -glyoxylsäuremethylester-trans-O-methyloxime
V
Figure imgf000136_0001
V
Figure imgf000136_0001
. 0. 0
Eine Mischung von 1,8 g (8,7 mmol) (2-Methyl- pyridyl-3) -glyoxylsäuremethylester-trans-O-methyloxim,A mixture of 1.8 g (8.7 mmol) of methyl (2-methyl-pyridyl-3) -glyoxylate-trans-O-methyloxime,
1,7 g (9,6 mmol) N-Bromsuccinimid und einer Spatelspitze Azoisobutyrodinitril in 30 ml CC14 wird ca. 4 Stunden mit einer 300 W UV-Lampe bestrahlt, wobei sich die Reaktions- mischung auf Rückflußtemperatur erwärmt. Anschließend verdünnt man die Reaktionsmischung mit Methylenchlorid und extrahiert die organische Phase mit Wasser. Die organische Phase wird mit Wasser extrahiert, über MgS04 getrocknet und eingeengt. Der Rückstand wird säulen¬ chromatographisch mit Cyclohexan/Essigester-Gemischen gereinigt. Man erhält 1,1 g (44 %) der TitelVerbindung als helles Öl.1.7 g (9.6 mmol) of N-bromosuccinimide and a spatula tip of azoisobutyrodinitrile in 30 ml of CC1 4 are irradiated for about 4 hours with a 300 W UV lamp, the reaction mixture heating to reflux temperature. The reaction mixture is then diluted with methylene chloride and the organic phase is extracted with water. The organic phase is extracted with water, dried over MgS0 4 and concentrated. The residue is purified by column chromatography using cyclohexane / ethyl acetate mixtures. 1.1 g (44%) of the title compound are obtained as a pale oil.
!H-NMR (CDC13; δ in ppm): ! H-NMR (CDC1 3 ; δ in ppm):
8,65 (d, breit, IH, Pyridyl); 7,55 (d, breit, IH, Pyridyl); 7,3 (t, breit, IH, Pyridyl); 4,4 (s, 2H, CH2Br); 4,1 (s, 3H, OCH3) ; 3,9 (s, 3H, OCH3) .8.65 (d, broad, IH, pyridyl); 7.55 (d, broad, IH, pyridyl); 7.3 (t, broad, IH, pyridyl); 4.4 (s, 2H, CH 2 Br); 4.1 (s, 3H, OCH 3 ); 3.9 (s, 3H, OCH 3 ).
f) 2-Oximino-l- (2' ,4' -dichlorphenyl) -propan-1-onf) 2-oximino-l- (2 ', 4' -dichlorophenyl) propan-1-one
Eine Mischung von 60 g (0,296 mol) 2,4-Dichlorpropiophe- non in 500 ml Toluol wird bei -10 bis -20°C mit 81 ml ge- sättigter etherischer Salzsäurelösung und anschließend bei der gleichen Temperatur mit einer Lösung von 33,3 g (0,323 mol) 2, 4-Dichlorpropiophenon in 150 ml Ether ver¬ setzt. Anschließend rührt man die Reaktionsmischung 4 Stunden bei -10°C und 14 Stunden bei Raumtemperatur. Dann extrahiert man die Reaktionsmischung mit Eiswasser und anschließend fünfmal mit ln NaOH. Die vereinigten al' kaiischen Phasen werden mit 20 %iger Schwefelsäure auf pH 5 angesäuert, wobei das Produkt auskristallisiert. Der Festkörper wird abfiltriert und in Methylenchlorid gelöst und die organische Phase wird über MgS04 getrocknet und eingeengt. Als Rückstand erhält man 63,1 g (42 %) der Titelverbindung als hellen FEstkörper.A mixture of 60 g (0.296 mol) of 2,4-dichloropropiophenone in 500 ml of toluene is mixed at -10 to -20 ° C. with 81 ml of saturated ethereal hydrochloric acid solution and then at the same temperature with a solution of 33.3 g (0.323 mol) of 2,4-dichloropropiophenone in 150 ml of ether. The reaction mixture is then stirred for 4 hours at -10 ° C. and for 14 hours at room temperature. Then the reaction mixture is extracted with ice water and then five times with NaOH. The combined al 'quay phases are based on 20% sulfuric acid Acidified to pH 5, the product crystallizing out. The solid is filtered off and dissolved in methylene chloride and the organic phase is dried over MgSO 4 and concentrated. The residue obtained is 63.1 g (42%) of the title compound as a light solid.
iH-NMR (CDC13, δ in ppm): i H-NMR (CDC1 3 , δ in ppm):
8,8 (s, IH, OH); 7,4 (s, IH, Phenyl); 7,3 (m, 2H,8.8 (s, IH, OH); 7.4 (s, IH, phenyl); 7.3 (m, 2H,
Phenyl); 2,1 (s, 3H, CH3) .Phenyl); 2.1 (s, 3H, CH 3).
1-Methoximino-2-oximino-1- (2' , 4' -dichlorpheny1) -propan1-methoximino-2-oximino-1- (2 ', 4' -dichloropheny1) propane
Eine Mischung von 4,7 g (20 mmol)A mixture of 4.7 g (20 mmol)
2-Oximino-1- (2' ,4' -dichlorphenyl) -propan-1-on (Bei- spiel lf), 2,5 g (30 mmol) O-Methylhydroxylamin-hydro- chlorid und 4,8 g (60 mmol) Pyridin wird über Nacht bei Raumtemperatur und anschließend 8 Stunden bei 50°C ge¬ rührt. Sodann wird die Reaktionsmischung eingeengt und der Rückstand wird in Methylenchlorid aufgenommen. Die organische Phase wird mit verdünnter Salzsäure und Wasser gewaschen, über MgS04 getrocknet und eingeengt. Der Rück¬ stand kristallisiert und wird mit Hexan ausgerührt. Man erhält 3 g (57 %) der Titelverbindung als farblosen Fest¬ körper.2-oximino-1- (2 ', 4' -dichlorophenyl) propan-1-one (example lf), 2.5 g (30 mmol) O-methylhydroxylamine hydrochloride and 4.8 g (60 mmol) of pyridine is stirred overnight at room temperature and then at 50 ° C. for 8 hours. The reaction mixture is then concentrated and the residue is taken up in methylene chloride. The organic phase is washed with dilute hydrochloric acid and water, dried over MgS0 4 and concentrated. The residue crystallizes and is extracted with hexane. 3 g (57%) of the title compound are obtained as a colorless solid.
iH-NMR (CDC13, δ in ppm): i H-NMR (CDC1 3 , δ in ppm):
8,25 (s, IH, OH); 7,4 (s, IH, Phenyl); 7,25 (d, breit, IH, Phenyl); 7,0 (d, IH, Phenyl); 3,9 (s, 3H, OCH3); 2,15 (S, 3H, CH3) .8.25 (s, IH, OH); 7.4 (s, IH, phenyl); 7.25 (d, broad, IH, phenyl); 7.0 (d, IH, phenyl); 3.9 (s, 3H, OCH 3 ); 2.15 (S, 3H, CH 3).
Figure imgf000137_0001
Figure imgf000137_0001
Eine Mischung von l g (3,8 mmol) 1-Meth- oximino-2-oximino-l- (2' ,4' -dichlorphenyl) -propan (Bei¬ spiel lg) in 20 ml Dimethylformamid wird mit 0,12 g (5 mmol) Natriumhydrid versetzt, man rührt bis die Ga- sentwicklung beendet ist und gibt anschließend 1,1 gA mixture of 1 g (3.8 mmol) of 1-methoximino-2-oximino-1- (2 ', 4' -dichlorophenyl) propane (example 1 g) in 20 ml of dimethylformamide is mixed with 0.12 g ( 5 mmol) of sodium hydride are added, the mixture is stirred until the evolution of gas has ended and 1.1 g are then added
(3,8 mmol) (2-Brommethylpyridyl-3) -glyoxylsäuremethyl¬ ester-trans-O-methyloxim (Beispiel le) hinzu. Man rührt eine Stunde bei Raumtemperatur, verdünnt die Reaktionsmi¬ schung anschließend mit Wasser und extrahiert die wäßrige Phase dreimal mit Methyl-t-butylether. Die vereinigten organischen Phasen werden über MgS04 getrocknet und ein¬ geengt. Der Rückstand wird säulenchromatographisch mit Cyclohexan/Essigester-Gemischen gereinigt. Das Produkt kristallisiert und wird mit Hexan ausgerührt. Man erhält 0,35 g (20 %) der TitelVerbindung als farblosen Festkör¬ per (FP = 111°C) .(3.8 mmol) (2-bromomethylpyridyl-3) -glyoxylsäuremethyl¬ ester-trans-O-methyloxime (example le) added. You stir one hour at room temperature, the reaction mixture is then diluted with water and the aqueous phase is extracted three times with methyl t-butyl ether. The combined organic phases are dried over MgSO 4 and concentrated. The residue is purified by column chromatography using cyclohexane / ethyl acetate mixtures. The product crystallizes and is extracted with hexane. 0.35 g (20%) of the title compound is obtained as a colorless solid (FP = 111 ° C.).
XH-NMR (CDC13, δ in ppm): X H-NMR (CDC1 3 , δ in ppm):
8,55 (s, breit, IH, Pyridyl); 7,55 (d, breit, IH; Pyridyl); 7,35 (s, breit, IH, Phenyl), 7,3 (dd, IH, Pyridyl); 7,15 (d, breit, IH, Phenyl); 6,9 (d, IH, Phenyl); 5,05 (s, 2H, OCH2) ; 4,05 (s, 3H, OCH3) ; 3,9 (s,8.55 (s, broad, IH, pyridyl); 7.55 (d, broad, IH; pyridyl); 7.35 (s, broad, IH, phenyl), 7.3 (dd, IH, pyridyl); 7.15 (d, broad, IH, phenyl); 6.9 (d, IH, phenyl); 5.05 (s, 2H, OCH 2); 4.05 (s, 3H, OCH 3 ); 3.9 (s,
3H, OCH3); 3,85 (s, 3H, OCH3) ; 2,15 (s, 3H, CH3) .3H, OCH 3 ); 3.85 (s, 3H, OCH 3 ); 2.15 (s, 3H, CH 3).
Beispiele zur Wirkung gegen SchadpilzeExamples of the action against harmful fungi
Die fungizide Wirkung der Verbindungen der Formel I ließ sich durch folgende Versuche zeigen:The fungicidal activity of the compounds of the formula I was demonstrated by the following tests:
Die Wirkstoffe wurden als 10 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cyclohexanon, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) und 10 Gew.-% Emulphor® EL (Emulan® EL, Emulgator auf der Basis ethoxylierter Fettalkohole) aufberei¬ tet und entsprechend der gewünschten Konzentration mit Wasser verdünnt.The active ingredients were given as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight. % Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) is prepared and diluted with water in accordance with the desired concentration.
A) Wirksamkeit gegen WeizenmehltauA) Efficacy against powdery mildew
Blätter von in Töpfen gewachsenen Weizenkeimlingen der SorteLeaves of potted wheat seedlings of the variety
"Frühgold" wurden mit wäßriger Spritzbrühe, die mit einer Stamm- lösung aus 10 % Wirkstoff, 63 % Cyclohexanon und 27 % Emulgier¬ mittel angesetzt wurde, besprüht und 24 Stunden nach dem Antrock¬ nen des Spritzbelages mit Sporen des Weizenmehltaus (Erysiphe graminis var. tri tici) bestäubt. Die Versuchspflanzen wurden an¬ schließend im Gewächshaus bei Temperaturen zwischen 20 und 22°C und 75 bis 80 % relativer Luftfeuchtigkeit aufgestellt. Nach 7 Tagen wurde das Ausmaß der Mehltauentwicklung visuell in % Befall der gesamten Blattfläche ermittelt. In diesem Test zeigten die mit 250 ppm der Verbindungen Nr. 1.2, 1.3, 1.4, 1.6, 1.7, 1.8 und 1.9 behandelten Pflanzen maximal 15 % Befall, während die unbehandelten Pflanzen zu 75 % befallen waren."Early gold" was sprayed with an aqueous spray mixture which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier, and 24 hours after the spray coating had dried on, with spores of the powdery mildew (Erysiphe graminis var . tri tici) pollinated. The test plants were then placed in a greenhouse at temperatures between 20 and 22 ° C. and 75 to 80% relative atmospheric humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area. In this test, the plants treated with 250 ppm of the compounds No. 1.2, 1.3, 1.4, 1.6, 1.7, 1.8 and 1.9 showed a maximum of 15% infection, while the untreated plants were 75% infected.
B) Wirksamkeit gegen Plasmopara vi ti colaB) Efficacy against Plasmopara vi ti cola
Blätter von Topfreben der Sorte "Müller-Thurgau" wurden mit wä߬ riger Spritzbrühe, die mit einer Stammlösung aus 10 % Wirkstoff, 63 % Cyclohexanon und 27 % Emulgiermittel angesetzt wurde, be¬ sprüht. Um die Dauerwirkung der Substanzen beurteilen zu können, wurden die Pflanzen nach dem Antrocknen des Spritzbelages für 7 Tage im Gewächshaus aufgestellt. Erst dann wurden die Blätter mit einer wäßrigen Zoosporenaufschwemmung von Plasmopara vi ticola inokuliert. Danach wurden die Reben zunächst für 48 Stunden in einer wasserdampfgesättigten Kammer bei 24°C und anschließend für 5 Tage im Gewächshaus bei Temperaturen zwischen 20 und 30°C aufge¬ stellt. Nach dieser Zeit wurden die Pflanzen zur Beschleunigung des Sporangienträgerausbruchs abermals für 16 Stunden in eine feuchte Kammer gestellt. Dann wurde das Ausmaß der Befallsent¬ wicklung auf den Blattunterseiten visuell ermittelt.Leaves of potted vines of the "Müller-Thurgau" variety were sprayed with an aqueous spray mixture which was prepared with a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. In order to be able to assess the long-term effect of the substances, the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara vi ticola. Thereafter, the vines were first placed for 48 hours in a steam-saturated chamber at 24 ° C. and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.
In diesem Test zeigten die mit 250 ppm der Verbindungen Nr. 1, 1.2, 1.3, 1.4, 1.6 und 1.9 behandelten Pflanzen maximal 15 % Be- fall, während die unbehandelten Pflanzen zu 70 % befallen waren.In this test, the plants treated with 250 ppm of the compounds No. 1, 1.2, 1.3, 1.4, 1.6 and 1.9 showed a maximum of 15% infection, while the untreated plants were 70% infected.
Beispiele zur Wirkung gegen tierische SchädlingeExamples of action against animal pests
Die Wirkung der Verbindungen der allgemeinen Formel I gegen tierische Schädlinge ließ sich durch folgende Versuche zeigen: Die Wirkstoffe wurdenThe activity of the compounds of the general formula I against animal pests was demonstrated by the following tests: The active compounds were
a) als 0,1 %-ige Lösung in Aceton odera) as a 0.1% solution in acetone or
b) als 10 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cyclo¬ hexanon, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxy¬ lierter Alkylphenole) und 10 Gew.-% Emulphor® EL (Emulan® EL, Emulgator auf der Basis ethoxylierter Fettalkohole)b) as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10 % By weight Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols)
aufbereitet und entsprechend der gewünschten Konzentration mit Aceton im Fall von a) bzw. mit Wasser im Fall von b) verdünnt.processed and diluted according to the desired concentration with acetone in the case of a) or with water in the case of b).
Nach Abschluß der Versuche wurde die jeweils niedrigste Konzen- tration ermittelt, bei der die Verbindungen im Vergleich zu unbe¬ handelten Kontrollversuchen noch eine 80 - 100 %-ige Hemmung bzw. Mortalität hervorriefen (Wirkschwelle bzw. Minimalkonzentration) . After the end of the tests, the lowest concentration was determined, at which the compounds still caused an 80-100% inhibition or mortality compared to untreated control tests (active threshold or minimum concentration).

Claims

Patentansprüche claims
1. Pyridylessigsaurederivate der Formel I1. Pyridylacetic acid derivatives of the formula I.
Rm— P' fl- CH20N = CR2 CR3 = NOR4 Rm- P ' fl- CH 2 0N = CR 2 CR 3 = NOR 4
COYR1 in der die Substituenten und der Index die folgende Bedeutung haben:COYR 1 in which the substituents and the index have the following meaning:
X N0CH3, CH0CH3, CHCH3 und CHCH2CH3;X N0CH 3 , CH0CH 3 , CHCH 3 and CHCH 2 CH 3 ;
Y Sauerstoff oder NR' ;Y is oxygen or NR ';
R' Wasserstoff oder Cι~C4-Alkyl;R 'is hydrogen or -C ~ C 4 alkyl;
R Cyano, Nitro, Trifluormethyl, Halogen, Cχ-C4-Alkyl und Cχ-C4-Alkoxy;R cyano, nitro, trifluoromethyl, halogen, Cχ-C 4 alkyl and Cχ-C 4 alkoxy;
m 0, 1 oder 2, wobei die Reste R verschieden sein können, wenn m für 2 steht;m is 0, 1 or 2, where the radicals R can be different if m is 2;
R1 Wasserstoff und C!-C4-Alkyl;R 1 is hydrogen and C ! -C 4 alkyl;
R2 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Halogen,R 2 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
Cι-C4-Alkyl, Cι-C4-Halogenalkyl, Cι-C4-Alkoxy, Cχ-C4-Ha- logenalkoxy, Cι~C4-Alkylthio, Cι-C4-Alkylamino oder Di-Ci-C4-alkylamino;Cι-C 4 -alkyl, C 4 haloalkyl, Cι-C4-alkoxy, Cχ-C logenalkoxy 4 -Ha-, Cι ~ C 4 alkylthio, Cι-C 4 alkylamino or di-Ci-C 4 -alkylamino;
R3 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Halogen,R 3 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
Cι-C6-Alkyl, Ci-Ce-Alkoxy, Cι-C6-Alkylthio, Cι-C6-Alkyl- amino, Di-Ci-Cβ-alkylamino, C2-C6-Alkenyl, C2-C6-Alkenyl- oxy, C2-C6-Alkenylthio, C2-C6-Alkenylamino, N-C2-C6-Alke- nyl-N-Ci-Cδ-alkylamino, C2-C6-Alkinyl, C2-C6-Alkinyloxy, C2-C6-Alkinylthio, C2-C6-Alkinylamino, N-C2-C6-Alkinyl- Cι-C6 alkyl, Ci-Ce-alkoxy, Cι-C 6 alkylthio, Cι-C amino 6 alkyl, di-Ci-Cβ alkylamino, C 2 -C 6 alkenyl, C 2 -C6- Alkenyloxy, C 2 -C 6 alkenylthio, C 2 -C 6 alkenylamino, NC 2 -C 6 alkenyl-N-Ci-C δ -alkylamino, C 2 -C 6 alkynyl, C 2 - C 6 alkynyloxy, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylamino, NC 2 -C 6 alkynyl-
N-Cι-C6-alkylamino, wobei die Kohlenwasserstoffreste dieser Gruppen partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Reste tragen können: Cyano, Nitro, Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Ci-Cß-Alkyl- aminocarbonyl, Di-Ci-Cö-alkylaminocarbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Ci-Cö-alkylaminothio- carbonyl, Cι-C6-Alkylsulfonyl, Ci-Cβ-Alkylsulfoxyl, Cι-C6-Alkoxy, Cι-C6~Halogenalkoxy, Cι-C6-Alkoxycarbonyl, Ci-Cβ-Alkylthio, Cι-C6-Alkylamino, Di-Ci-Cβ-alkylamino, C2-C6-Alkenyloxy, C3-C6-Cycloalkyl, C3-C6-Cycloalkyloxy,N--C 6 -alkylamino, where the hydrocarbon radicals of these groups can be partially or completely halogenated or can carry one to three of the following radicals: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci C ß -alkyl aminocarbonyl, di-Ci-C ö -alkylaminocarbonyl, Ci-Cβ-alkylaminothiocarbonyl, di-Ci-Cö-alkylaminothio-carbonyl, Cι-C 6 -alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, Cι-C 6 -alkoxy, Cι-C 6 ~ haloalkoxy, Cι-C 6 -alkoxycarbonyl, Ci-Cβ-alkylthio, Cι-C 6 alkylamino, di-Ci-Cβ-alkylamino, C 2 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy,
Heterocyclyl, Heterocyclyloxy, Aryl, Aryloxy, Aryl-Cι-C4-alkoxy, Arylthio, Aryl-Cι-C4-alkylthio, Hetaryl, Hetaryloxy, Hetaryl-Cι-C4-alkoxy, Hetarylthio, Hetaryl-Cι-C4-alkylthio, wobei die cyclischen Reste ihrerseits partiell oder vollständig halogeniert sein können und/oder ein bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Cι-C6-Alkyl, Cι-C6-Ha- logenalkyl, Ci-Cβ-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C3C6-Cycloalkyl, Cι-C6-Alkoxy, Cι-C6-Halogenalkoxy,Heterocyclyl, Heterocyclyloxy, Aryl, Aryloxy, Aryl-Cι-C 4 -alkoxy, Arylthio, Aryl-Cι-C 4 -alkylthio, Hetaryl, Hetaryloxy, Hetaryl-Cι-C 4 -alkoxy, Hetarylthio, Hetaryl-Cι-C 4 - alkylthio, where the cyclic radicals in turn can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C 1 -C 6 alkyl, Cι- C 6 -Ha- logenalkyl, Ci-Cβ alkylsulfonyl, Cι-C 6 alkylsulfoxyl, C 3 C 6 cycloalkyl, Cι-C 6 -alkoxy, C 6 haloalkoxy,
Ci-Cδ-Alkoxycarbonyl, Ci-Cβ-Alkylthio, Ci-Cδ-Alkylamino, Di-Ci-Cβ-alkylamino, Ci-Ce-Alkylaminocarbonyl, Di-Ci-Cö-alkylaminocarbonyl, Cι-C6-Alkylaminothiocarbonyl, Di-Cι-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Al- kenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio,Ci-C δ- alkoxycarbonyl, Ci-Cβ-alkylthio, Ci-C δ- alkylamino, di-Ci-Cβ-alkylamino, Ci-Ce-alkylaminocarbonyl, di-Ci-C ö -alkylaminocarbonyl, Cι-C 6 -alkylaminothiocarbonyl, Di-Cι-C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio,
Hetaryl, Hetaryloxy, Hetarylthio und C (=NORa) -An-Rb;Hetaryl, hetaryloxy, hetarylthio and C (= NOR a ) -A n -R b ;
C3-C6-Cycloalkyl, C3-C6-Cycloalkyloxy, C3-C6-Cycloalkyl- thio, C3-C6-Cycloalkylamino, N-C3-C6-Cycloalkyl-N-Cι-C6- alkylamino, C3-C6-Cycloalkenyl, C3-C6-Cycloalkenyloxy,C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, C 3 -C6 cycloalkylamino, NC 3 -C 6 cycloalkyl-N--C-C 6 - alkylamino, C 3 -C 6 cycloalkenyl, C 3 -C 6 cycloalkenyloxy,
C3-C6-Cycloalkenylthio, C3-C6-Cycloalkenylamino, N-C3-C6- Cycloalkenyl-N-Ci-Cö-alkylamino, Heterocyclyl, Hetero¬ cyclyloxy, Heterocyclylthio, Heterocyclylamino, N-Hetero- cyclyl-N-Cι-C6-alkylamino, Aryl, Aryloxy, Arylthio, Aryl- amino, N-Aryl-N-Cx-Ce-alkylamino, Hetaryl, Hetaryloxy,C 3 -C 6 cycloalkenylthio, C 3 -C 6 cycloalkenylamino, NC 3 -C 6 - cycloalkenyl-N-Ci-C ö alkylamino, heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylamino, N-heterocyclic-N -C-C 6 alkylamino, aryl, aryloxy, arylthio, arylamino, N-aryl-N-Cx-Ce-alkylamino, hetaryl, hetaryloxy
Hetarylthio, Hetarylamino, N-Hetaryl-N-Cι-C6-alkylamino, wobei die cyclischen Reste partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halo¬ gen, Cι-C6-Alkyl, Ci-Cβ-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C3-Ce-Cycloalkyl, Cι-C6-Alkoxy, Cχ-C6-Halogenalkoxy, Ci-Cδ-Alkoxycarbonyl, Cι-C6-Alkyl- thio, Cx-Cβ-Alkylamino, Di-Cx-Cö-alkylamino, Cι-C6-Alkyl- aminocarbonyl, Di-Ci-Cβ-alkylaminocarbonyl, Ci-Cδ-Alkyl- aminothiocarbonyl, Di-Cι-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy, C(=NORa)-An-Rb oder NRf-C0-Hetarylthio, hetarylamino, N-hetaryl-N -CC-C 6 -alkylamino, where the cyclic radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl , Aminothiocarbonyl, Halo¬ gene, -C-C 6 alkyl, Ci-Cβ-haloalkyl, -C-C 6 alkylsulfonyl, Cι-C 6 alkylsulfoxyl, C 3 -Ce cycloalkyl, Cι-C 6 alkoxy, Cχ- C 6 -haloalkoxy, Ci-C δ -alkoxycarbonyl, Cι-C 6 -alkyl-thio, Cx-Cβ-alkylamino, di-Cx-C ö -alkylamino, Cι-C 6 -alkyl aminocarbonyl, di-Ci-Cβ -alkylaminocarbonyl, Ci-C δ -alkyl aminothiocarbonyl, Di-Cι-C 6 -alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy, C (= NOR a ) -A n -R b or NR f -C0-
D-R<3; Wasserstoff,DR <3; Hydrogen,
Cι-Cιo-Alkyl, C2-Cι0-Alkenyl, C2-Cι0-Alkinyl, Cι-C10-Alkyl- carbonyl, C2-Cιo-Alkenylcarbonyl, C3-Cιo-Alkinylcarbonyl oder Cχ-Cιo-Alkylsulfonyl, wobei diese Reste partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Amino¬ thiocarbonyl, Halogen, Ci-Cβ-Alkyl, Ci-Cβ-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C!-C6-Alkoxy,Cι-Cιo-alkyl, C 2 -Cι 0 -alkenyl, C 2 -Cι 0 -alkynyl, Cι-C 10 -alkylcarbonyl, C 2 -Cιo-alkenylcarbonyl, C 3 -Cιo-alkynylcarbonyl or Cχ-Cιo-alkylsulfonyl , where these radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino thiocarbonyl, halogen, Ci-Cβ-alkyl, Ci-Cβ- Haloalkyl, -C 6 alkyl sulfonyl, -C 6 alkyl sulfoxyl, C ! -C 6 alkoxy,
Ci-Cβ-Halogenalkoxy, Ci-Cö-Alkoxycarbonyl, Ci-Cβ-Alkyl- thio, Cx-Cg-Alkylamino, Di-Cx-Ce-alkylamino, Cι-C6-Alkyl- aminocarbonyl, Di-Ci-Cö-alkylaminocarbonyl, Cι-C6-Alkyl- aminothiocarbonyl, Di-Ci-Ce-alky]aminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, C3-C6-Cycloalkyl,Ci-Cβ-haloalkoxy, Ci-C ö -alkoxycarbonyl, Ci-Cβ-alkylthio, Cx-Cg-alkylamino, di-Cx-Ce-alkylamino, Cι-C 6 -alkyl aminocarbonyl, di-Ci-C ö -alkylaminocarbonyl, -C-C 6 alkyl aminothiocarbonyl, di-Ci-Ce-alky] aminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl,
C3-C6-Cycloalkyloxy, Heterocyclyl , Heterocyclyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy und Hetarylthio, wobei die cyclischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkyl- sulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, Ci-Cö-Halogen- alkoxy, Ci-Cδ-Alkyloxycarbonyl, Cι-C6-Alkylthio, C1-C6-AI- kylamino, Di-Cι-C6-Alkylamino, Cι-C6-Alkylaminocarbonyl, Di-Ci-Cβ-Alkylaminocarbonyl, Cι-C6-Alkylaminothiocarbonyl, Di-Ci-Cδ-Alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Al- kenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio oder C (=N0Ra) -An-Rb;C 3 -C 6 cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano , Nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Cι-C 6 -haloalkyl, Cι-C 6 -alkylsulfonyl, Cι-C 6 -alkyl sulfoxyl, C 3 -C 6 -cycloalkyl, -CC 6 alkoxy, Ci-C ö -haloalkoxy, Ci-C δ -alkyloxycarbonyl, -C-C 6 -alkylthio, C 1 -C 6 -AI- alkylamino, di-Cι-C 6 -Alkylamino, -C-C 6 -alkylaminocarbonyl, Di-Ci-Cβ-alkylaminocarbonyl, Cι-C 6 -alkylaminothiocarbonyl, Di-Ci-C δ -alkylaminothiocarbonyl, C 2 -C 6 -alkenyl, C 2 -C 6 -Al- kenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C (= NO R a ) -A n -R b ;
C3-C6-Cycloalkyl, Aryl, Arylcarbonyl, Arylsulfonyl, Hetaryl, Hetarylcarbonyl oder Hetarylsulfonyl, wobei diese Reste partiell oder vollständig halogeniert sein können oder einen bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylcarbonyl, Cx-Cg-Alkylsul- fonyl, Cι-C6-Alkylsulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alk- oxy, Ci-Cß-Halogenalkoxy, Cι-C6-Alkyloxycarbonyl,C 3 -C 6 cycloalkyl, aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl , Aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Cι-C 6 -haloalkyl, Cι-C 6 -alkylcarbonyl, Cx-Cg-alkylsulfonyl, Cι-C 6 -alkyl sulfoxyl, C 3 -C 6 -cycloalkyl, Cι-C 6 -alk- oxy, Ci-C ß haloalkoxy, Cι-C 6 alkyloxycarbonyl,
Cι-C6-Alkylthio, Cι-C6-Alkylamino, Di-Cι-C6-Alkylamino, Cι-C6-Alkylaminocarbonyl, Di-Cι-C6-Alkylaminocarbonyl, Cι-C6-Alkylaminothiocarbonyl, Di-Cι-C6-Alkylaminothio- carbonyl, C2-C6~Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyl- oxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy, C (=NORa)-An-Rb oder NRf-CO-D-R9; wobeiC 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl, di C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-Cι- C 6 -alkylaminothiocarbonyl, C 2 -C 6 ~ alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy, C (= NOR a ) -A n -R b or NR f -CO-D-R9; in which
für Sauerstoff, Schwefel oder Stickstoff steht und wobei der Stickstoff Wasserstoff oder Ci-Ce-Alkyl trägt;represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or Ci-Ce-alkyl;
D eine direkte Bindung, Sauerstoff oder NRh;D is a direct bond, oxygen or NR h ;
n 0 oder 1 bedeutet;n represents 0 or 1;
Ra Wasserstoff oder Cι-C6-Alkyl bedeutet undR a is hydrogen or -CC 6 alkyl and
Rb Wasserstoff oder Cι-C6-Alkyl bedeutet,R b is hydrogen or -CC 6 alkyl,
Rf Wasserstoff, Hydroxy, Ci-Cβ-Alkyl, C:-C6-Alkenyl, C2-C6-Alkinyl, Cι-C6-Alkoxy, C2-C6-Alkenyloxy, C2-C6-Alki- nyloxy, Cι-C6-Alkoxy-Cι-C6-alkyl, Ci-C6-Alkoxy-Cι-C6-al- koxy und Ci-Cg-Alkoxycarbonyl;R f is hydrogen, hydroxy, Ci-Cβ-alkyl, C : -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alky - nyloxy, C 6 -C 6 alkoxy-C 6 C 6 alkyl, C 1 -C 6 alkoxy C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl;
R9, Rh unabhängig voneinander Wasserstoff, Ci-Cβ-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl, C3-C6-Cy- cloalkenyl, Aryl, Aryl-Ci-Cβ-alkyl, Hetaryl und Hetaryl- Cι-C6-alkyl;R9, R h independently of one another are hydrogen, Ci-Cβ-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, aryl, Aryl-Ci-Cβ-alkyl, hetaryl and hetaryl -C-C 6 alkyl;
sowie deren Salze.as well as their salts.
2. Verbindungen der Formel I gemäß Anspruch 1, in denen R2, R3 und R4 die folgende Bedeutung haben:2. Compounds of formula I according to claim 1, in which R 2 , R 3 and R 4 have the following meaning:
R2 Wasserstoff, Hydroxy, Cyclopropyl, Halogen, Cι-C4-Alkyl, C1-C4-Alkoxy oder Cι-C4-Alkylthio,-R 2 is hydrogen, hydroxy, cyclopropyl, halo, Cι-C 4 alkyl, C 1 -C 4 alkoxy or Cι-C 4 alkylthio, -
R3 Wasserstoff, Hydroxy, Halogen, Cyclopropyl, Cyclohexyl, Cι-C4-Alkyl, Cι-C4-Alkoxy, C1-C4-Alkylthio,R 3 is hydrogen, hydroxyl, halogen, cyclopropyl, cyclohexyl, Cι-C 4 -alkyl, C 4 alkoxy, C 1 -C 4 alkylthio,
Aryl oder Hetaryl, wobei diese Gruppen partiell oder vollständig halogeniert sein können oder ein bis 3 der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Aminothio¬ carbonyl, Halogen, Ci-Cg-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkylsulfoxyl, C3-C6-Cyclo- alkyl, Ci- C6-Alkoxy, Cι-C6-Halogenalkoxy, Cι-C6-Alkoxy- carbonyl, Ci-Cβ-Alkylthio, Cι-C6-Alkylamino, Di-Cι~C6- alkylamino, Ci-Cδ-Alkylaminocarbonyl, Di-Ci-Cö-alkylamino- carbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Ci-Cβ-alkyl- aminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy,Aryl or hetaryl, where these groups can be partially or completely halogenated or can carry one to 3 of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl, Cι -C 6 -haloalkyl, -C-C 6 -alkylsulfonyl, -C-C 6 -alkylsulfoxyl, C 3 -C 6 -cycloalkyl, Ci- C 6 -alkoxy, Cι-C 6 -haloalkoxy, -C-C 6 -alkoxy - Carbonyl, Ci-Cβ-alkylthio, -C-C 6 alkylamino, Di-Cι ~ C 6 - alkylamino, Ci-C δ -alkylaminocarbonyl, Di-Ci-C ö alkylamino carbonyl, Ci-Cβ-alkylaminothiocarbonyl, Di -Ci-Cβ-alkyl aminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy,
Benzyl, Benzyloxy, Aryl, Aryloxy, Hetaryl und Hetaryloxy; Wasserstoff,Benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy; Hydrogen,
Cι-Cιo-Alkyl, C3-C6-Cycloalkyl, C2-Cι0-Alkenyl, C2-Cι0- Alkinyl, Cι-Cιo-Alkylcarbonyl, C2-Cιo-Alkenylcarbonyl, C3-C10-Alkinylcarbonyl oder Ci-Cirj-Alkylsulfonyl, wobei diese Gruppen partiell oder vollständig halogeniert sein können oder ein bis 3 der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Cι-C6-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylsulfonyl, Cι-C6-Alkyl- sulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, Ci-Cö-Halogen- alkoxy, Cι-C6-Alkoxycarbonyl, Ci-Cβ-Alkylthio, Cι-C6- Alkylamino, Di-Cι-C6-alkylamino, Cι-C6-Alkylaminocarbonyl, Di- Cι-C6-alkylaminocarbonyl, Cι-C6-Alkylaminothio- carbonyl, Di-Cι-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl,Cι-Cιo-alkyl, C 3 -C 6 cycloalkyl, C 2 -Cι 0 -alkenyl, C 2 -Cι 0 -alkynyl, Cι-Cιo-alkylcarbonyl, C 2 -Cιo-alkenylcarbonyl, C 3 -C 10 -alkynylcarbonyl or Ci-Cirj-alkylsulfonyl, where these groups can be partially or completely halogenated or can carry one to 3 of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 alkyl , -C-C 6 -haloalkyl, -C-C 6 -alkylsulfonyl, Cι-C 6 -alkyl-sulfoxyl, C 3 -C 6 -cycloalkyl, Cι-C 6 -alkoxy, Ci-C ö -haloalkoxy, Cι- C 6 -alkoxycarbonyl, Ci-Cβ-alkylthio, -C-C 6 - alkylamino, di-Cι-C 6 -alkylamino, Cι-C 6 -alkylaminocarbonyl, di-Cι-C 6 -alkylaminocarbonyl, Cι-C6-alkylaminothio-carbonyl , Di-Cι-C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl,
C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Aryl¬ thio, Hetaryl, Hetaryloxy und Hetarylthio, wobei die aromatischen und heteroaromatischen Reste ihrerseits partiell oder vollständig halogeniert sein können und/ oder ein bis drei der folgenden Gruppen tragen können:C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the aromatic and heteroaromatic radicals can in turn be partially or completely halogenated and / or can carry one to three of the following groups :
Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, Ci-Cβ-Alkyl, Cx-C6-Halogenalkyl, Cι-C6-Alkylsulfonyl , Cι-C6-Alkyl- sulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, Ci-Cδ-Halogen- alkoxy, Cι-C6-Alkyloxycarbonyl, Cι-C6-Alkylthio, Cι-C6-Cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, C x -C 6 haloalkyl, Cι-C 6 -alkylsulfonyl, Cι-C 6 -alkylsulfoxyl, C 3 -C 6 -cycloalkyl, -C-C 6 -alkoxy, Ci-Cδ-haloalkoxy, -C-C 6 -alkyloxycarbonyl, Cι-C 6 -alkylthio, Cι-C 6 -
Alkylamino, Di-Cι-C6-Alkylamino, C-.-C6-Alkylaminocarbonyl, Di-Ci-Cß-Alkylaminocarbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Ci-Cβ-Alkylaminothiocarbonyl, C;>-C6-Alkenyl, C2-C6~ Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio oder C (=NORa) -An-Rb;Alkylamino, di-C 6 alkylamino, C- . -C 6 -Alkylaminocarbonyl, Di-Ci-C ß -Alkylaminocarbonyl, Ci-Cβ-Alkylaminothiocarbonyl, Di-Ci-Cβ-Alkylaminothiocarbonyl, C;> - C 6 -Alkenyl, C 2 -C6 ~ Alkenyloxy, Benzyl, Benzyloxy, Aryl , Aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C (= NOR a ) -A n -R b ;
Aryl, Hetaryl, Arylcarbonyl, Hetarylcarbonyl, Arylsulfo- nyl oder Hetarylsulfonyl, wobei diese Gruppen partiell oder vollständig halogeniert sein können oder ein bis 3 der folgenden Gruppen tragen können: Cyano, Nitro,Aryl, hetaryl, arylcarbonyl, hetarylcarbonyl, arylsulfonyl or hetarylsulfonyl, where these groups can be partially or completely halogenated or can carry one to 3 of the following groups: cyano, nitro,
Hydroxy, Merkapto, Amino, Carboxyl, Aminocarbonyl, Amino¬ thiocarbonyl, Halogen, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkylcarbonyl, Cj.-C6-Alkylsulfonyl, Cι-C6-Alkyl- sulfoxyl, C3-C6-Cycloalkyl, Cι-C6-Alkoxy, Cι-C6-Halogen- alkoxy, Cι-C6-Alkoxycarbonyl, Cι-C6-Alkylthio, Cι-C6-Hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino thiocarbonyl, halogen, Ci-Cβ-alkyl, Cι-C 6 haloalkyl, Cι-C 6 alkylcarbonyl, Cj. -C 6 -Alkylsulfonyl, -C-C 6 -alkyl-sulfoxyl, C 3 -C 6 -cycloalkyl, -C-C 6 -alkoxy, -C-C 6 -haloalkoxy, -C-C 6 -alkoxycarbonyl, Cι-C 6 -Alkylthio, Cι-C 6 -
Alkylamino, Di-Cι-C6-alkylamino, Cj-Cβ-Alkylaminocarbonyl, Di-Cι-C6-alkylaminocarbonyl, Cι-C6-Alkylaminothiocarbonyl, Di-Ci-Cδ-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6- Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy oder C (=N0Ra) -An-Rb. Alkylamino, di-Cι-C6 alkylamino, Cj-Cβ-alkylaminocarbonyl, di-Cι-C 6 alkylaminocarbonyl, Cι-C 6 -Alkylaminothiocarbonyl, di-Ci-C δ -alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 - alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NO R a ) -A n -R b .
3. Verbindungen der Formel I gemäß Anspruch 1, in denen Y für NR' und X für NOCH3 steht.3. Compounds of formula I according to claim 1, in which Y is NR 'and X is NOCH 3 .
4. Verbindungen der Formel I gemäß Anspruch 1, in denen m für 0 steht.4. Compounds of formula I according to claim 1, in which m is 0.
5. Verbindungen der Formel I gemäß Anspruch 1, in denen R1 für Methyl steht.5. Compounds of formula I according to claim 1, in which R 1 is methyl.
6. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R2 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II6. A process for the preparation of the compounds of the formula I according to claim 1, in which R 2 is not halogen, characterized in that a benzyl derivative of the formula II
^
Figure imgf000145_0001
in der L1 für eine nucleophil austauschbare Abgangsgruppe steht, in an sich bekannter Weise mit einem Hydroxyimim der Formel III^
Figure imgf000145_0001
in which L 1 represents a nucleophilically exchangeable leaving group, in a manner known per se with a hydroxyimime of the formula III
R4ON=C(R3) C(R2) = NOH III umsetzt.R 4 ON = C (R 3 ) C (R 2 ) = NOH III.
7. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R2 und R3 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II gemäß Anspruch 1 in an sich bekannter Weise mit einem Dihydroxyimim der Formel IV7. A process for the preparation of the compounds of formula I according to claim 1, in which R 2 and R 3 is not halogen, characterized in that a benzyl derivative of the formula II according to claim 1 in a manner known per se with a dihydroxyimime of the formula IV
HON=C(R3) C(R2) = NOH IV zu einer Verbindung der Formel VHON = C (R 3 ) C (R 2 ) = NOH IV to a compound of formula V
^
Figure imgf000145_0002
^
Figure imgf000145_0002
COYR1 umsetzt und V anschließend mit einer Verbindung der Formel VIImplemented COYR 1 and V then with a compound of formula VI
R4 L1 VI in der L2 für eine nucleophil austauschbare Abgangsgruppe steht, zu I umsetzt.R 4 L 1 VI in which L 2 represents a nucleophilically exchangeable leaving group, converts to I.
8. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R2 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II gemäß Anspruch 1 in an sich bekannter Weise mit einem Carbonyl¬ hydroxyimin der Formel VII8. A process for the preparation of the compounds of the formula I according to claim 1, in which R 2 is not halogen, characterized in that a benzyl derivative of the formula II according to claim 1 is known in a manner known per se with a carbonyl hydroxyimine of the formula VII
0=C(R3) C(R2) = NOH VII zu einer Verbindung der Formel VIII 0 = C (R 3 ) C (R 2 ) = NOH VII to a compound of formula VIII
Figure imgf000146_0001
Figure imgf000146_0001
umsetzt, VIII anschließend entwederimplements VIII then either
a) zunächst mit Hydroxylamin oder dessen Salz und danach mit einer Verbindung der Formel VI (R4-L2) gemäß Anspruch 7 odera) first with hydroxylamine or its salt and then with a compound of formula VI (R 4 -L 2 ) according to claim 7 or
b) mit einem Hydroxylamin oder einem Hydroxylammoniumsalz der Formel IXa bzw. IXbb) with a hydroxylamine or a hydroxylammonium salt of the formula IXa or IXb
R4 ONH2 R4 ONH3® Qθ R 4 ONH 2 R 4 ONH 3 ® Q θ
IXa IXb in der Q® für das Anion einer Säure steht,IXa IXb in which Q® represents the anion of an acid,
zu I umsetzt.converts to I.
9. Verfahren zur Herstellung der Verbindungen I gemäß9. Process for the preparation of the compounds I according to
Anspruch 1, in denen Y für Sauerstoff steht (IA) , dadurch gekennzeichnet, daß man einen Methylpyridincarbonsäureester der allgemeinen Formel XClaim 1, in which Y represents oxygen (IA), characterized in that a methylpyridinecarboxylic acid ester of the general formula X
Figure imgf000146_0002
in der Rx für Cχ-C4-Alkyl steht, in an sich bekannter Weise in den entsprechenden Methylenpyridincarbonsäureester der allge¬ meinen Formel XI
Figure imgf000147_0001
überführt, XI anschließend durch Umsetzung mit einem Hydro- xyimin der Formel III gemäß Anspruch 6 in den entsprechenden Pyridincarbonsäureester der allgemeinen Formel XII
Figure imgf000146_0002
in which R x is Cχ-C 4 alkyl, in a manner known per se in the corresponding methylenepyridinecarboxylic acid ester of the general formula XI
Figure imgf000147_0001
transferred, XI then by reaction with a hydroxyimine of the formula III according to claim 6 in the corresponding pyridinecarboxylic acid ester of the general formula XII
Figure imgf000147_0002
überführt, XII zum Alkohol XIII
Figure imgf000147_0002
transferred XII to alcohol XIII
Figure imgf000147_0003
Figure imgf000147_0003
OH reduz iert , XII I zum Pyridinaldehyd XIVOH reduced, XII I to pyridine aldehyde XIV
Figure imgf000147_0004
oxidiert, XIV in an sich bekannter Weise in das Cyanhydrin XV
Figure imgf000147_0004
oxidized, XIV in a conventional manner in the cyanohydrin XV
Figure imgf000147_0005
Figure imgf000147_0005
CN überführt, XV anschließend zum entsprechenden Mandelsäure- ester XVICN transferred, XV then to the corresponding mandelic ester XVI
Figure imgf000147_0006
hydrolysiert , XVI zum α-Ketoester XVII
Figure imgf000147_0006
hydrolyzed, XVI to the α-ketoester XVII
Figure imgf000147_0007
oxidiert und XVII anschließend in an sich bekannter Weise entweder
Figure imgf000147_0007
oxidized and then XVII either in a conventional manner
a) mit O-Methylhydroxylamin (H2N0CH3) oder einem O-Methyl- 5 hydroxylammoniumsalz, odera) with O-methylhydroxylamine (H 2 N0CH 3 ) or an O-methyl- 5 hydroxylammonium salt, or
b) mit einem Ethylen-Wittig- oder -Wittig-Horner Reagens, oderb) with an ethylene-Wittig or -Wittig-Horner reagent, or
10 c) mit einem Methoxy-Wittig- oder -Wittig-Horner Reagens10 c) with a methoxy-Wittig or -Wittig-Horner reagent
in den entsprechenden Pyridylessigsäureester IA überführt.transferred to the corresponding pyridylacetic acid ester IA.
10. Verfahren zur Herstellung der Verbindungen I gemäß An-10. Process for the preparation of the compounds I according to
15 spruch 1, in denen Y für NR' steht (IB) , dadurch gekennzeich¬ net, daß man den entsprechenden Pyridylessigsäureester der Formel IA gemäß Anspruch 9 in an sich bekannter Weise mit einem Amin der Formel XVIII15 claim 1, in which Y is NR '(IB), characterized gekennzeich¬ net that the corresponding pyridylacetic acid ester of formula IA according to claim 9 in a conventional manner with an amine of formula XVIII
20 HNR'R1 XVIII umsetzt. 20 HNR'R 1 XVIII implemented.
11. Verfahren zur Herstellung der Verbindungen I gemäß Anspruch 25 1, dadurch gekennzeichnet, daß man ein Hydroxylaminderivat der Formel Ila11. A process for the preparation of the compounds I according to claim 25 1, characterized in that a hydroxylamine derivative of the formula Ila
Figure imgf000148_0001
in an sich bekannter Weise mit einer Carbonylverbindung der Formel Vlla
Figure imgf000148_0001
in a manner known per se with a carbonyl compound of the formula VIIa
3535
0=C(R2) C(R3) =NOR4 Vlla umsetzt.0 = C (R 2 ) C (R 3 ) = NOR 4 Vlla implemented.
40 12. Verfahren zur Herstellung der Verbindungen I gemäß Anspruch40 12. A process for the preparation of the compounds I according to claim
1, in denen Y für Sauerstoff steht (IA) , dadurch gekennzeich¬ net, daß man einen Methylpyridincarbonsäureester der Formel X1, in which Y represents oxygen (IA), characterized gekennzeich¬ net that a methylpyridinecarboxylic ester of the formula X
Figure imgf000148_0002
in der Rx für Cχ-C4-Alkyl steht, in an sich bekannter Weise zum Alkohol der Formel XHIa
Figure imgf000148_0002
in which R x is Cχ-C 4 alkyl, in a manner known per se to the alcohol of the formula XHIa
Figure imgf000149_0001
Figure imgf000149_0001
OH reduziert, XHIa zum Pyridinaldehyd XlVaOH reduced, XHIa to pyridine aldehyde XlVa
Figure imgf000149_0002
oxidiert, XlVa in an sich bekannter Weise in das Cyanhydrin XVa
Figure imgf000149_0002
oxidized, XlVa in a conventional manner in the cyanohydrin XVa
Figure imgf000149_0003
überführt, XVa anschließend zum Mandelsäureester XVIa
Figure imgf000149_0003
transferred, XVa then to the mandelic acid ester XVIa
Figure imgf000149_0004
hydrolysiert, XVIa zum α-Ketoester XVIIa
Figure imgf000149_0004
hydrolyzed, XVIa to the α-ketoester XVIIa
XVIIa
Figure imgf000149_0005
oxidiert und XVIIa anschließend in an sich bekannter Weise entwederXVIIa
Figure imgf000149_0005
oxidized and then XVIIa either in a manner known per se
a) mit O-Methylhydroxylamin (H2N0CH3) oder einem O-Methyl- hydroxylammoniumsalz, odera) with O-methylhydroxylamine (H 2 N0CH 3 ) or an O-methylhydroxylammonium salt, or
b) mit einem Ethylen-Wittig- oder -Wittig-Horner Reagens, oderb) with an ethylene-Wittig or -Wittig-Horner reagent, or
c) mit einem Methoxy-Wittig- oder -Wittig-Horner Reagens in den entsprechenden Pyridylessigsäureester XVIIIa, XVIIIb bzw. XVIIIcc) with a methoxy-Wittig or -Wittig-Horner reagent in the corresponding pyridylacetic acid esters XVIIIa, XVIIIb and XVIIIc
Figure imgf000150_0001
Figure imgf000150_0001
XVI I Ia XVI IIb XVI I IcXVI I Ia XVI IIb XVI I Ic
10 überführt, XVIIIa, XVIIIb bzw. XVIIIc anschließend in an sich bekannter Weise zu den Benzylhalogeniden XlXa, XlXb bzw. XlXc10 transferred, XVIIIa, XVIIIb and XVIIIc then in a conventional manner to the benzyl halides XlXa, XlXb and XlXc
Figure imgf000150_0002
Figure imgf000150_0002
XlXa XlXb XIXcXlXa XlXb XIXc
, wobei Hai für Chlor oder Brom steht, halogeniert und XlXa, 20 XlXb bzw. XIXc anschließend durch Umsetzung mit einem Hydro¬ xyimin der Formel III gemäß Anspruch 6 in den entsprechenden Pyridylessigsäureester IA überführt., where shark is chlorine or bromine, halogenated and XlXa, 20 XlXb or XIXc then converted into the corresponding pyridylacetic acid ester IA by reaction with a hydroxyimine of the formula III according to claim 6.
13. Zwischenprodukte der Formel II gemäß Anspruch 6. 2513. Intermediates of formula II according to claim 6. 25
14. Zwischenprodukte der Formel VIII gemäß Anspruch 8.14. Intermediates of formula VIII according to claim 8.
15. Zwischenprodukte der Formeln XII, XIII, XIV, XV, XVI und XVII gemäß Anspruch 9.15. Intermediates of the formulas XII, XIII, XIV, XV, XVI and XVII according to claim 9.
3030
16. Zwischenprodukte der Formel Ila gemäß Anspruch 11.16. Intermediates of formula Ila according to claim 11.
17. Zwischenprodukte der Formeln XVa, XVIa, XVIIa, XVIIIa, XVIIIb und XVIIIc gemäß Anspruch 12.17. Intermediates of the formulas XVa, XVIa, XVIIa, XVIIIa, XVIIIb and XVIIIc according to claim 12.
3535
18. Mittel gegen tierische Schädlinge oder Schadpilze, enthaltend übliche Zusatzstoffe und eine wirksame Menge einer Verbindung der Formel I gemäß Anspruch 1.18. Agents against animal pests or harmful fungi, containing customary additives and an effective amount of a compound of the formula I according to claim 1.
40 19. Mittel nach Anspruch 18 zur Bekämpfung tierischer Schädlinge aus der Klasse der Insekten, Spinntiere oder Nematoden.40 19. Composition according to claim 18 for controlling animal pests from the class of insects, arachnids or nematodes.
20. Verfahren zur Bekämpfung von tierischen Schädlingen oder20. Procedures for controlling animal pests or
Schadpilzen, dadurch gekennzeichnet, daß man die Schädlinge 45 oder Schadpilze, deren Lebensraum oder die von ihnen frei¬ zuhaltenden Pflanzen, Flächen, Materialien oder Räume mit einer wirksamen Menge einer Verbindung der Formel I gemäß Anspruch 1 behandelt.Harmful fungi, characterized in that the pests 45 or harmful fungi, their habitat or the plants, surfaces, materials or spaces to be kept free of them are also included treated an effective amount of a compound of formula I according to claim 1.
21. Verwendung der Verbindungen I gemäß Anspruch 1 zur Her- Stellung von Mitteln gegen tierische Schädlinge oder Schad¬ pilze.21. Use of the compounds I according to claim 1 for the preparation of agents against animal pests or harmful fungi.
22. Verwendung der Verbindungen I gemäß Anspruch 1 zur Bekämpfung von tierischen Schädlingen und Schadpilzen. 22. Use of the compounds I according to claim 1 for combating animal pests and harmful fungi.
PCT/EP1996/004676 1995-11-03 1996-10-28 Pyridylacetic acid derivatives, method and intermediate products for producing them and agents containing them WO1997017328A1 (en)

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DE59605803T DE59605803D1 (en) 1995-11-03 1996-10-28 PYRIDYL ACETIC DERIVATIVES, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND MEANS CONTAINING THEM
EP96937262A EP0876344B1 (en) 1995-11-03 1996-10-28 Pyridylacetic acid derivatives, method and intermediate products for producing them and agents containing them
AU74941/96A AU7494196A (en) 1995-11-03 1996-10-28 Pyridylacetic acid derivatives, method and intermediate products for producing them and agents containing them
US09/068,002 US5965587A (en) 1995-11-03 1996-10-28 Pyridylacetic acid derivatives, their preparation, intermediates for their preparation and compositions containing them
AT96937262T ATE195729T1 (en) 1995-11-03 1996-10-28 PYRIDYLESTIC ACID DERIVATIVES, PROCESSES AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION THEREOF AND MATERIALS CONTAINING THEM
JP9517797A JPH11514658A (en) 1995-11-03 1996-10-28 Pyridylacetic acid derivative, method for producing the same, intermediate product for producing the same, and composition containing the same

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WO1995021153A1 (en) * 1994-02-04 1995-08-10 Basf Aktiengesellschaft Phenyl acetic acid derivatives, process and intermediate products for their production and agents containing them
WO1995021154A2 (en) * 1994-02-04 1995-08-10 Basf Aktiengesellschaft Phenyl acetic acid derivatives, process and intermediate products for their production and agents containing them
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